With women comprising nearly 50% of HIV/AIDS infections globally, the development of new woman-initiated HIV prevention methods has become a public health imperative. To date, the female condom and the diaphragm are the only woman-initiated prevention methods available on the consumer market. Recent research has focused on two HIV/AIDS prevention technologies undergoing clinical trials: microbicides and tenofovir (PrEP). Both are being touted as female-initiated HIV/AIDS prevention technologies that women can use covertly, without a partner's knowledge, to improve their odds in protecting themselves against HIV. Use of these new technologies will not only depend on their effectiveness, but on women's willingness to use these products. This cross-sectional study used an integrative conceptual model that included both intrapersonal and interpersonal constructs to explore factors associated with women's intentions to use. Three hundred and forty-eight high-risk women in Toronto, Canada completed self-administered questionnaires (SAQs). Results were remarkably consistent across relationship types and prevention methods examined in the study, with 60% of the women intending to use microbicides and tenofovir. Women who perceived themselves to be at greater risk for STIs, had greater microbicide self-efficacy, and more positive perceptions of microbicides were more likely to intend to use microbicides. Women with ≤ grade 12 education, greater sexual and HIV risk, greater tenofovir self-efficacy and more positive perceptions of tenofovir were more likely to intend to use tenofovir. When asked which method they preferred, 66% preferred pre-exposure prophylaxis (PrEP). Women, who had previously used a barrier method for contraception, had greater microbicide self-efficacy and more positive perceptions of microbicides were less likely to prefer tenofovir. Women, who had used hormonal methods for contraception, had greater tenofovir self-efficacy and more positive perceptions of tenofovir were more likely to prefer tenofovir. Findings have important implications including assisting researchers in the development and refinement of these products and consumer analysts in the development of marketing strategies that highlight method attributes women perceive positively. Findings will also help health care providers identify women who would potentially use these products and assist women in developing confidence in their ability to effectively use such methods.