Limited access, poor experience, and high out-of-pocket (OOP) costs of primary care services may lead to avoidable emergency department (ED) presentations. But, the evidence has been limited with most of the studies using surveys conducted in EDs. Using detailed health survey data of Australian women linked to multiple administrative datasets, we extend the literature by estimating the effects of access, costs, and experience of general practice (GP) services on the probability of ED attendance while accounting for a large set of health and socioeconomic covariates. Our findings suggest that improvements in access to primary care services can significantly reduce the demand for low acuity ED presentations. We also show that the impact of increased accessibility of GP services is expected to be the highest for socioeconomic vulnerable populations and patients whose access is the poorest. This evidence can be useful for the design of targeted policies aimed at improving access to doctors in particular areas that are socioeconomically disadvantaged and where medical skill shortages are significant. However, policies aimed at reduction in primary care OOP costs or improvement in the perception of GP quality are less likely to be effective in reducing the number of non-urgent ED presentations.