Measuring the density of alcohol outlets around schools is a critical step towards understanding the drivers of drinking among adolescents. Different methodologies have been used in the literature for this purpose, but the implications of using one methodology or another have not been clearly assessed. Our aim was to compare different methods to measure alcohol outlet density and highlight under which characteristics of the environment might be best using each approach. We used Geographic Information Systems to geolocate schools (n = 576) and alcohol outlets (n = 21,732) in Madrid. We defined the density of alcohol outlets as the number of establishments within an area of 400 m around schools measured using two buffering methods: crow flies’ and street network distances. We evaluated the agreement between both methods visually and through regression models, including street connectivity, population density, and density of recreational venues as predictors of disagreement. The density of alcohol outlets around schools was higher using crow flies’ distances compared to street network distances. The differences between methodologies were wider in areas of higher density of outlets, especially in the downtown areas, where there are higher population density and street connectivity. Our results suggest that the spatial characteristics and morphology of the study area (e.g., street connectivity and population density) should be considered when deciding the methodology to be used to measure alcohol outlet density. Future studies should explore the implications of different exposure measures in their association with drinking prevalence and consumption patterns among different geographical contexts.