In 2005, Faith Hill returned with her new country album, Fireflies. The CD debuted on top of the Billboard Country and all genre album charts, placing her among only a handful of artists to have three consecutive albums debut at number one on both charts. The debut single, "Mississippi Girl", became Hill's highest-debuting single. The song was written specifically for her by John Rich (of Big and Rich) and Adam Shoenfield of MuzikMafia, and tells the abbreviated story of her life. Hill recorded two other songs by Rich, "Sunshine and Summertime" and "Like We Never Loved at All", both of which became successful singles. The title track, "Stealing Kisses" and "If You Ask" were written by artist Lori McKenna and also appear on McKenna's albums. The album marked a return to Hill's country roots and succeeded in reestablishing her place on country radio. Her focus changed to charitable endeavors in 2005. In the days immediately following Hurricane Katrina, Hill and her husband, who was raised in Louisiana, joined groups taking supplies to Gulfport, Mississippi. The two also hosted several charity concerts to benefit those who were displaced by the storm. Later in the year the couple established the Neighbor's Keeper Foundation, which provides funding for community charities to assist with basic humanitarian services in the event of a natural disaster or for desperate personal circumstances.

After a six-year break from touring following the birth of her youngest daughter, in 2006 Hill and husband Tim McGraw embarked on their Soul2Soul II Tour 2006. The tour became the highest grossing country music tour ever with a gross of $90 million. It was named "Major Tour of the Year" by the prestigious Pollstar Magazine, beating out such heavyweights as Madonna and the Rolling Stones. In a special gesture, the couple donated all of the profits from their performance in New Orleans to Hurricane Katrina relief.

In 2007, Hill started work on her first domestic greatest hits package, titled The Hits, which was released on October 2. The Hits features two new songs, "Lost" and "Red Umbrella", plus a live version of the song "Stronger," taken from the Soul2Soul 2007 tour. The album also features hits covering her entire career from 1993–2005. Included with The Hits is a DVD of 11 of Hill's music videos. The album has sold 265,000 copies in the US. Hill also recorded a duet called "Sleeping with the Telephone" for Reba McEntire's Duets album, released on September 18, 2007. She's also featured on husband Tim McGraw's 2007 album Let It Go. She sings two duets with him, "I Need You" and "Shotgun Rider". Both songs were sung at the couple's critically acclaimed Soul2Soul II Tour 2006. She and Tim also did an encore of their Soul2Soul II Tour; Soul2Soul 2007 began in June and ran through August. The song I Need You has been nominated twice at the 2008 Grammy Awards for Best Country Collaboration with Vocals and Best Country Song. The show took place at the Staples Center in Los Angeles, CA on February 10, 2008 but the song didn't win. In 2007 Faith Hill took over as the signature voice of NFL on NBC's Sunday Night Football, singing the theme song.

• "Ghost Whisperer" (1 episode, 2008)
       - Ghost in the Machine (2008) TV episode (performer: "Red Umbrella" (uncredited))
• "CMT Top 20 Countdown" (4 episodes, 2007-2008)
       - Episode dated 3 January 2008 (2008) TV episode (performer: "Peace in the Valley")
       - Best of 2007 (2007) TV episode (performer: "I Need You")
       - Episode dated 13 December 2007 (2007) TV episode (performer: "Peace in the Valley")
       - Episode dated 6 December 2007 (2007) TV episode (performer: "Peace in the Valley")
• Elvis: Viva Las Vegas (2007) (TV) (performer: "Peace in the Valley")
• "CMT Giants" (1 episode, 2006)
       - Reba (2006) TV episode (performer: "You Lie")
• 40th Annual Country Music Association Awards (2006) (TV) (performer: "Stealing Kisses")
  ... aka 40th Annual CMA Awards (USA: informal title)
• "CMT Insider" (1 episode, 2006)
       - 2006 CMA Nominee Report (2006) TV episode (performer: "Like We Never Loved at All")
• "Cold Case" (1 episode, 2006)
       - Dog Day Afternoons (2006) TV episode (performer: "Breathe")
• Chasing Liberty (2004) (performer: "If I'm Not in Love")
• "The Sopranos" (1 episode, 2002)
       - Mergers and Acquisitions (2002) TV episode (performer: "Breathe")
• "Saturday Night Live" (1 episode, 2002)
  ... aka NBC's Saturday Night (USA: first season title)
  ... aka SNL (USA: informal title)
  ... aka SNL 25 (USA: alternative title)
  ... aka Saturday Night (USA: second season title)
  ... aka Saturday Night Live '80 (USA: sixth season title)
  ... aka The Best of Saturday Night Live (USA: rerun title)
       - Sarah Michelle Gellar/Faith Hill (2002) TV episode (performer: "Lonesome Day", "You're Missing")
• The 74th Annual Academy Awards (2002) (TV) (performer: "There You'll Be")
• Pearl Harbor (2001) (performer: "There You'll Be")