- "Kickapoo" (4:14)
- "Classico" (0:58)
- "Baby" (1:36)
- "Destiny" (0:37)
- "History" (1:42)
- "The Government Totally Sucks" (1:34)
- "Master Exploder" (2:24)
- "The Divide" (0:22)
- "Papagenu (He's My Sassafrass)" (2:24)
- "Dude (I Totally Miss You" (2:53)
- "Break In-City (Storm the Gate!)" (1:22)
- "Car Chase City" (2:42)
- "Beelzeboss (The Final Showdown)" (5:35)
- "POD" (2:32)
- "The Metal" (2:45)
The two songs on the album, "History" and "Baby", predate the writing of the album, and were written in the 1990s. Gass has claimed that History was one of the first songs he ever wrote with Black. The song "Papagenu (He's My Sassafrass)", partially uses the same melody as the song "Sasquatch", a song which features on their TV series, and has not been officially released elsewhere.
In December 2004, Tenacious D toured Australia and New Zealand whilst Black was in the continent filming King Kong. On this tour, they debuted the songs "Kickapoo", "Dude (I Totally Miss You)" and "Kong". In June 2005, "The Government Totally Sucks", "Master Exploder" and "POD" were debuted at a benefit show in Los Angeles. In September 2005, "Papagenu (He's My Sassafrass)" was debuted at another Los Angeles benefit show.
The song "Beelzeboss (The Final Showdown)" was the last song to be written for the album, and was done so in either late 2005 or early-mid 2006. This was due to the film ending being changed, and this new song was required.
The album was recorded in 2005 and 2006. Footage from the recording can be seen on the documentary, Recording the Rock, which was released on the DVD for the film in early 2007.
- "Kickapoo" - Liam Lynch
- "Classico" - Johann Sebastian Bach, Ludwig van Beethoven, Wolfgang Amadeus Mozart
- "Papagenu (He's My Sassafrass)" - John King
- "Break In-City (Storm the Gate!)" - Lynch, King
- "Car Chase City" - John Konesky, John Spiker, King
- "Beelzeboss (The Final Showdown)" - Dave Grohl, Lynch
- "The Metal" - Konesky
- "Kickapoo" - Meat Loaf and Ronnie James Dio
- "The Government Totally Sucks" - JR Reed as "Lee"
- "Papagenu (He's My Sassafrass)" - John C. Reilly as "Sasquatch"
- "Car Chase City" - Paul F. Tompkins
- "Beelzeboss (The Final Showdown)" - Dave Grohl as "Satan"
The album was released on the 14th November 2006, a few days prior to the release of the movie, and three days before the band started The Pick of Destiny Tour. The band held a signing at the Virgin Megastore in New York on the day of release.
Epic Records had a deal with iTunes for the release of the album to feature exclusive content. A short film called Tenacious D: Time Fixers was released on iTunes. The first half of the episode was available for free, however, if the album was pre-ordered, the second half could be downloaded. Both versions have since been made available on Tenacious D's official VEVO page on VEVO.com and YouTube. An acoustic recording of "Rock Your Socks", released on their 2001 album, was also downloadable when the album was pre-ordered, and was included with the album on iTunes after release. It is now no longer available.
A clean version of the album was released on CD at the same time as the explicit CD. This version is almost the exact same as the regular release, however the swears are replaced with funnier words. The CD contains a holographic front cover and any explicit photographs on the inside booklet of the album (middle fingers, penises) are pixelated out. The CD doesn't state anywhere on it that it is the clean version, however the parental advisory logos are removed on the front and back. The clean version is available on select digital stores.
- In the 2012 music video for Rize of the Fenix, a stack of (presumably unsold) Pick of Destiny CDs can be seen at the start of the video, whilst the lyric in the song references the poor box office sales of the film.
- In November 2013, Tenacious D performed "Classico" live for the first time at the FunFunFun Festival in Austin, Texas. They now play the song frequently at their acoustic concerts.
- In 2014, the album was re-released on vinyl on the 15th December 2014, and again on the 18th August 2017. The digital download card came with an acoustic recording of the song "It's Late", a song written and performed by the band in the 1990s.