We analyzed biomarker validation data of unprotected sex from women in Zimbabwe to determine whether condom and sexual behavior misreporting differs between users of different contraceptive methods. Self-reported sexual behavior was compared with the presence of prostate-specific antigen (PSA) in vaginal fluid, a biomarker of semen exposure. Of the 195 women who were PSA positive, 94 (48 %) reported no sex or only condom-protected sex. Hormonal contraceptive users misreported sexual behavior less than women using non-hormonal methods (45 vs. 67 %, P = 0.03). This misclassification pattern could have implications on the elevated risk of HIV infection associated with hormonal contraception in some studies.