About the song, Billy Corgan said it was "A simple song in a country tuning" and was the first song written by Corgan after the Siamese Dream tour. The guitars recorded in the song are tuned to EGBGBE half a step down. The drum machine track is exactly the same track Corgan recorded when he laid down the demo version of the song, because he "couldn't remember how to recreate it".
Corgan joked on an August 24, 2000 taping of VH1Storytellers that he planned on making "Thirty-Three", "Sixty-Six", and "Ninety-Nine", but only finished "Thirty-Three".
When the band released their greatest hits collection in 2001, Thirty-Three made neither the international nor the US version. It was included, however, for the Greatest Hits Video Collection.
At the time of its release, the plan to release the song as the album's final single was a point of disagreement for insiders. Sources close to the band claim that "Muzzle" was in fact due to be released as the final single, as is evidenced by the fact that a promotional single for the song was issued to radio stations worldwide.
The music video for "Thirty-Three", directed both by Billy Corgan and then-girlfriend Yelena Yemchuk, is a series of images shot in stop-motion, ending with a re-enactment of the Mellon Collie album cover. Jimmy Chamberlin is notably absent from shots of the band. Because the group's videos so often avoid the literal interpretation of lyrics, the video for "Thirty-Three" was created with images closely related to the words of the song, as an intentional stylistic departure.