Aim: Our aim was to examine the association between emergency dental care use and dental providers’ availability and ZIP code social vulnerability index. Methods: This cross-sectional observational study mapped variations in emergency dental care and analyzed their association with social vulnerability using generalized spatial two-stage least-squares to address spatial correlation. To perform spatial autoregressive modeling to examine how dental provider capacity and social vulnerability influence emergency care use across neighboring counties, accounting for ZIP Code Tabulation Area (ZCTA) spillover effects, we used secondary data from the Maryland Health Services Cost Review Commission, InfoUSA, and the US Census American Community Survey. We focused on emergency dental care usage in ZIP Code Tabulation Areas, using emergency department visits and inpatient stays per 1000 residents for dental conditions, as the dependent variable. Results: Highly vulnerable ZCTAs saw 5.9× more non-traumatic dental condition (NTDC) ED visits, 5.3× more chronic dental ED visits, 3.3× more NTDC inpatient stays, and 1.3× more chronic dental inpatient stays than less vulnerable areas. For all four measures of emergency dental care use, increased dental provider availability was associated with reductions in use of emergency dental care (ED), while higher social vulnerability was associated with increased use. For example, an increase of one dental provider per 1000 residents was associated with a reduction of 28.2 non-traumatic dental ED visits, while a high social vulnerability index was associated with an increase of 88.6 non-traumatic dental ED visits. Conclusions: There was an association among dental provider availability, social vulnerability, and the use of emergency dental care.