Starting right at the beginning, before even Arnold Layne, Roger and Nick met each other when Roger asked to borrow Nick's car.
The band's first lineup (under the name The Tea Set) included a guitarist called Bob Klose who didn't last long.
Walk With Me Sydney is the first song written by Roger Waters, predating Take Up Thy Stethoscope And Walk. It can be found on the first disc of the Early Years boxset.
Syd and David had been friends for years before Floyd. Gilmour attended a different school, but still lived in Cambridge. Before being chosen to replace Syd, Gilmour played in a band called Jokers Wild.
Arnold Layne was written about a real person.
See Emily Play was originally called Games For May, after a psychedelic event Pink Floyd played at.
Pink Floyd got in trouble for Matilda Mother and had to change some of the lyrics because it plagiarised a book by a popular author at the time.
Whilst Piper was written almost entirely by Syd, there are two notable exceptions: Interstellar Overdrive is the first song to credit the entire band (and the only one with the Syd-era lineup), and Take Up Thy Stethoscope was Roger's first song on an album. For comparison, the final song written by Roger on a Pink Floyd album was the underrated Two Suns In The Sunset.
Candy And A Current Bun (which appears on Relics) had to have it's lyrics changed because of drug references.
Point Me To The Sky (a non album single released before Saucerful, that ended up on Relics) is the first Floyd song to credit David Gilmour, and is also the first Waters-Gilmour collaboration.
The title track of A Saucerful of Secrets is the first song to credit the entire 'classic' lineup. It is also Gilmour's first credit on an album.
Let There Be More Light features David's first guitar solo on an album. It also mentions Mildenhall, where there was an RAF base. I don't know if it's still there, it's been over 60 years since the song was written.
The working title for See-Saw was 'The Most Boring Song I've Ever Heard'. (Source is the book 'The Story Behind Every Pink Floyd Song'). It ended up making the album anyway, just to be the one song no-one remembers from it. Maybe they had a point with the working title?
Remember A Day and See-Saw were both written by Rick Wright, and the former wouldn't feel out of place on Piper.
Set The Controls For The Heart of the Sun is allegedly the only song on which all five members played. The problem with verifying that is it's very hard to hear the guitars on the track due to the incredibly muddy mixing/production of the album. All we have is the word of the band on this one.
Jugband Blues might be Syd's final song on an album, but he also wrote an unreleased song (until the Early Years set, anyway) called Scream Thy Last Scream. That song just so happens to be the only song other than Corporal Clegg that Nick sang on. His line in One Of These Days is heavily distorted spoken word.
The More-Ummagumma era is a bit of a blind spot for me, but I do know that the songs used for The Man And The Journey are all taken from Saucerful through Ummagumma. It's why you sometimes hear Saucerful of Secrets called The Massed Gadgets Of Hercules.
On The Nile Song, David essentially invented metal vocals.
Around this time, Pink Floyd also wrote music for the film Zabriskie Point which ended up being rejected. Amongst the tracks recorded were Heart Beat Pig Meat and Come In Number 51, Your Time Is Up. The latter is a version of Careful With That Axe, Eugene.
Atom Heart Mother Suite is the final song to feature Nick's voice. He shouts 'SILENCE IN THE STUDIO!' during the Mind Your Throats section.
AHMS is also the third song to be credited to the entire band.
The rest of AHM features a song by each of Roger, David and Rick, with Nick having the main credit for Alan's Psychedelic Breakfast.
Meddle both starts and ends with wind, although it's not a loop. Although One Of These Days starts with wind then fades in, and Echoes ends with wind while fading out.
On the vinyl format, Echoes takes up the entire B-side of the record. The same is true for Atom Heart Mother's A-side being taken up by it's title track.
Echoes started out as a series of demos called 'Nothing', 'The Son of Nothing', 'Return of the Son of Nothing' and so on. The only known surviving demo out of these is Nothing Part 14, which appears on the Early Years box set.
Echoes misses out on being the longest Floyd song by mere seconds. Atom Heart Mother Suite barely edges it. Shine On would be their longest if it had been released as one whole song instead of being split into two halves.
The band were already playing early versions of Dark Side live before they did Obscured By Clouds for the film La Vallee. Indeed, Obscured By Clouds was done in a short time and is often completely forgotten, but is firmly inbetween Meddle and Dark Side, meaning Floyd released 3 albums in 3 years. It also means that the fans who think Meddle should be part of the 'Big 4' would need to expand it to a 'big 6' due to Obscured separating Meddle from Dark Side.
Dark Side went through quite a few iterations before the band settled on the version we have today. For example, Great Gig began life as The Mortality Sequence and featured phrases from the Bible and quotes from Apollo astronauts as opposed to Clare Torry's wailing. There was a song called The Travel Sequence that was most likely dropped for On The Run, versions of Any Colour You Like got up to 8 minutes long, Eclipse was the early name for the piece because a band called Medicine Head released an album called Dark Side of the Moon, but theirs flopped so Floyd decided to switch back to the original title.
Also around this time, Floyd attempted to make an album called Household Objects, but only ended up with two tracks as they decided it was too strange even for them. Wine Glasses would, however, see the light of day, as it can be heard at the start of Shine On parts 1-5.
I'm going to stop here as this is a lot of facts already and I could go on forever. The Wall would need it's own post, there are that many facts about it.