Health literacy is related to different health-related outcomes. However, the nature of the relationship between health literacy and health outcomes is not well understood. One pathway may lead from health literacy to health outcomes by means of access to healthcare. The goal of the current study is to explore the association between health literacy and the particular measure of access to healthcare—unmet medical need—for the first time in Croatia and, to the best of our knowledge, for the first time in the EU context. We use data obtained from face-to-face interviews in a large nationally representative sample of the Croatian population (n = 1000) to estimate the level of health literacy and self-reported access to care and investigate the association between health literacy and self-perceived barriers to access. Our study showed that limited and problematic health literacy is prevalent and associated with higher rates of unmet medical need. Unmet need is largely caused by long waiting lists. It is therefore essential to design health services fitting the needs of those who have limited and/or problematic health literacy as well as enhance health education with the potential of improving the access to care and health outcomes as well as design policies that reduce waiting times.