Tea & Sympathy comprised songs Fanning had written in his time with Powderfinger, as well as new content written after the band went on hiatus. Most of the writing was done in what Fanning described as a "creative burst" between March and May 2005. Much of the inspiration for the work on the album came from Fanning's reaction to the death of his brother in 2002, and to the ending of a 12-year relationship with his girlfriend, Philippa Sison. The majority of the album was recorded at Real World Studios with Tchad Blake in June 2005, except for "Not Finished Just Yet", "Believe", "Wash Me Clean", and "Hope & Validation", which were recorded at Fanning's Brisbane home. Fanning was supported by Brisbane musicians Jerry Marotta, Keith Duffy, and John Bedggood, who also formed part of his live band. The album was developed in a relaxed manner, with Fanning stating, "We had a ball putting the songs together."
Three singles were released from the album. The most successful of these was the lead single, "Wish You Well", shortly followed by "Songbird". These releases were only sold as digital download singles. The third single from the album, "Watch Over Me", was the only to be released as a CD single and achieved minor success on the Australian singles chart. It entered the chart on 9 July 2006 at No. 16, and spent eight weeks in the top 50. On 26 January 2006, "Wish You Well" was voted No. 1 for the Triple J Hottest 100, 2005. Following "Watch Over Me", Fanning digitally released a fourth single "Weekend of Mystery", which was not officially on the album, except for those who purchased the album from the iTunes Store. Fanning also took home the award for Best Music Video at the 2006 ARIA Awards for the iconic 'Wish You Well' clip.
On 2 December 2005, Fanning announced a nationwide Which Way Home Concert Tour, named after the song on the album of the same name. Fanning played seven shows between 25 February and 10 March 2006, in all of Australia's major capital cities. He was supported by Perth band The Panics and Brisbane singer Andrew Morris. He followed this with the "Yesterday's Gone" tour, announced on 11 August 2006, and concluding with Powderfinger re-uniting and returning to the recording studio. Fanning later stated that while he enjoyed making Tea & Sympathy, "Powderfinger is my real job".