Background: In low-income countries such as Benin, most people have poor access to healthcare services. There is scarcity of evidence about barriers to accessing healthcare services in Benin. Therefore, we examined the magnitude of the problem of access to healthcare services and its associated factors. Methods: We utilized data from the 2017–2018 Benin Demographic and Health Survey (n = 15,928). We examined the associations between the demographic and socioeconomic characteristics of women using multilevel logistic regression. The outcome variable for the study was problem of access to healthcare service. Adjusted odds ratios (AORs) with 95% confidence intervals (95% CI) were estimated. Results: Overall, 60.4% of surveyed women had problems in accessing healthcare services. Partner’s education (AOR = 0.70; 95% CI; 0.55–0.89), economic status (AOR = 0.59; 95% CI; 0.47–0.73), marital status (AOR = 0.44; 95% CI; 0.39–0.51), and parity (AOR = 1.85; 95% CI; 1.45–2.35) were significant individual-level factors associated with problem of access to healthcare. Region (AOR = 5.24; 95% CI; 3.18–8.64) and community literacy level (AOR = 0.69; 95% CI; 0.51–0.94) were the main community-level risk factors. Conclusions: Enhancing husband education through adult education programs, economic empowerment of women, enhancing national education coverage, and providing priority for unmarried and multipara women need to be considered. Additionally, there is the need to ensure equity-based access to healthcare services across regions.