Extant health literacy research is unclear about the contribution of health literacy to health behaviors and is limited regarding women’s health issues. The primary purpose of this study is to investigate the association between health literacy and five health behaviors (Pap smear screening, annual physical checkup, smoking, checking food expiration dates, and monitoring physical changes) in women and to test whether the association is mediated by health knowledge. A national sample of 1,754 female adults in Taiwan was included in the study. Result showed that health literacy was positively and independently related to checking food expiration dates and monitoring physical changes, and that health literacy was not related to physical checkup and Pap smear screening. Interestingly, women with high health literacy were more likely to be a current smoker. Study findings suggest that efforts to improve health promotion behaviors in women should consider health literacy as an important factor and that the effect of health literacy on health prevention behaviors may vary by women’s access to care.