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Custodio earned a Bachelor of Arts degree from the University of Puerto Rico and worked for various industries before landing a job in the accounting department of Prinair (Puerto Rico International Airlines). There she met Edwin Custodio, with whom she would eventually have two children. She later worked for the US Department of Defense (DoD) in Panama. With the support of her husband, she presented herself before Headquarters, Air Force Military Personnel Center (AFMPC) to apply for the United States Air Force Officer Training School. Upon admission, Custodio was accepted as a pilot candidate to become a United States Air Force pilot. She entered the Flight Screening Pilot Officer Training School in January 1980. After successful completion of Flight Screening she entered Officer Training School and was commissioned a Second Lieutenant. She qualified for Undergraduate Pilot Training (UPT) at Laughlin Air Force Base in Texas and graduated the following year, thus becoming the first Latina to complete the U.S