Maines was born in Lubbock, Texas, to country musician and producer Lloyd Maines and his wife Tina May Maines. She attended Williams Elementary School in Lubbock where her second grade teacher recalls being told by Maines during a math lesson, "Teacher, I don't need to learn this stuff--I'm gonna be a star." Maines was a cheerleader while attending O. L. Slaton Junior High School, and graduated in 1992 from Lubbock High School where she had participated in the school choir. Maines has described growing up in conservative Texas, saying "I always rebelled against that.

Maines had a public feud with fellow country music star Toby Keith over the 2002 chart-topping country hit "Courtesy of the Red, White and Blue", as well as a comment Maines made about U.S. President George W. Bush during a March 2003 Dixie Chicks concert in London.  Maines publicly criticized Keith's song "Courtesy of the Red, White and Blue" by saying, "I hate it. It's ignorant, and it makes country music sound ignorant. It targets an entire culture--and not just the bad people who did bad things. You've got to have some tact. Anybody can write, 'We'll put a boot in your ass.'" Keith responded by belittling Maines's songwriting skills with, "I'll bury her. She has never written anything that has been a hit" and, "That's what I do--I write songs." Keith further stated, "she said anyone can write 'We'll put a boot in your ass', but, you know ... she didn't."  After Maines commented at a March 2003 Dixie Chicks concert at the Shepherd's Bush Empire theatre in London that the Chicks didn't want the Iraq War and were "ashamed" President Bush "was from Texas", Keith's 2003 "Shock'n Y'all" tour began displaying a backdrop showing a doctored photo of Maines with Iraqi dictator Saddam Hussein. Shortly thereafter, on May 21, 2003, Maines wore a T-shirt with the letters "F.U.T.K." written on the front while performing for the Academy of Country Music Awards broadcast. The Dixie Chicks website stated that the letters stood for "Freedom, United, Together in Kindness." Some saw it as a veiled insult directed at Keith.  In August 2003, Keith publicly declared that he was done feuding with Maines, explaining, "You know, a best friend of mine ... lost a two-year-old daughter to cancer. ... [Recently] I saw ... a picture of me and Natalie and it said, 'Fight to the Death' or something. It seemed so insignificant. I said, 'Enough is enough.' ... People try to make everything black and white. I didn't start this battle. They started it with me; they came out and just tore me up. One thing I've never, ever done, out of jealousy or anything else, is to bash another artist and their artistic license."  In the 2006 documentary Dixie Chicks: Shut Up and Sing, backstage footage prior to her appearance wearing the F.U.T.K. shirt recorded the conversation between Maines and Simon Renshaw and confirmed that the original intent of the shirt was, in fact, a shot at Keith in response to his criticism of her: the letters stood for "Fuck You Toby Keith". As of January 2007, Keith continues to refuse to say Maines's name and argues that the doctored photo was intended to express his feeling that Maines's criticism was tyrannical and a dictator-like attempt to squelch Keith's free speech.

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