Policies to decrease low-acuity emergency department (ED) use have traditionally assumed that EDs are a substitute for unavailable primary care (PC). However, such policies can exacerbate ED overcrowding, rather than ameliorate it, if patients use EDs to complement, rather than substitute, their PC use. We tested whether Medicaid managed care enrolees visit the ED for nonemergent and PC treatable conditions to substitute for or to complement PC. Based on consumer choice theory, we modelled county-level monthly ED visit rate as a function of PC supply and used 2012–2015 New York Statewide Planning and Research Cooperative System (SPARCS) outpatient data and non-linear least squares method to test substitution vs complementarity. In the post-Medicaid expansion period (2014–2015), ED and PC are substitutes state-wide, but are complements in highly urban and poorer counties during nights and weekends. There is no evidence of complementarity before the expansion (2012–2013). Analyses by PC provider demonstrate that the relationship between ED and PC differs depending on whether PC is provided by physicians or advanced practice providers. Policies to reduce low-acuity ED use via improved PC access in Medicaid are likely to be most effective if they focus on increasing actual appointment availability, ideally by physicians, in areas with low PC provider supply. Different aspects of PC access may be differently related to low-acuity ED use.