Background: Prior regional studies of women Veterans identified barriers to Veterans Affairs (VA) healthcare use. However, these studies do not reflect the demographic profile of women Veterans nationally, recent advances in VA women’s healthcare, and the national context of expanded healthcare alternatives. Objective: To characterize health, VA perceptions, barriers, healthcare delivery preferences, and reasons for VA or non-VA healthcare use in a national women Veteran sample. Methods: Cross-sectional, population-based 2008–2009 National Survey of Women Veterans (n=3611). Results: VA users had worse physical and mental health than non–VA-only users and healthcare nonusers. Older women Veterans had worse physical health, whereas younger groups had worse mental health. Healthcare use was highest for dual users, followed by VA-only users, but did not differ by age group. Healthcare nonusers were most likely to lack a regular source for healthcare. Perceptions of VA care quality and sex-appropriateness were highest for VA-only, followed by dual, then non–VA-only users. VA perceptions were guided by personal experience for 90% of VA users, versus media or other secondhand sources for 70% of other groups. Non–VA-only users and healthcare nonusers had more knowledge gaps about VA and misperceptions about VA eligibility and services; non–VA-only users more likely encountered VA enrollment barriers. Conclusions: Many nonusers had healthcare needs that were not met. Positive VA perceptions by women with first-hand VA experience, contrasted with VA knowledge gaps by those without such exposure, suggests the need for more education about available VA healthcare services. VA planning should account for mental health needs and healthcare use by younger women Veterans.