Muñoz was born in Málaga, Andalusia in southern Spain and had a successful amateur career in both Europe and the United States.

Additionally, she was runner-up to Amanda Blumenherst at the 2008 U.S. Women's Amateur in Eugene, Oregon, and was a member of Europe's Junior Solheim Cup Team in 2002, 2003, and 2005.

At Arizona State, she was the 2008 NCAA Individual Champion in her junior year, winning by making a 25-foot (8 m) putt at the first hole of a playoff against UCLA's Tiffany Joh in Albuquerque, New Mexico.

After shooting a 64 (−9) in the final round, she won the three-round event on the first playoff hole, defeating former ASU teammate Anna Nordqvist with an eagle putt; Muñoz earned €50,000 and a three-year LET exemption.

[5] In her rookie season of 2010, Muñoz made the cut in her first eleven events, and won over $402,000 in LPGA competition with two top ten finishes.

[6] Muñoz handily won the competition for LPGA Tour Rookie of the Year with 704 points; the runner-up was compatriot Beatriz Recari with 419.