In the metropolises of China, the metro plays an increasingly important role in commuting because of its efficiency, affordability, and cleanliness. This paper attempts to explore the relationship between walking access distance to metro stations and the demographic characteristics of passengers, such as age, monthly income, travel frequency, gender, and travel purpose, as well as the influence of the urban context. Nanjing Metro Line 2 is selected as the case study. By using different methods such as a questionnaire survey, spatial decay function, analysis of covariance (ANOVA), network analysis of routes, and K-means cluster analysis, it is suggested that demographic characteristics have a significant impact on the pedestrian walking distance, with the exception of gender. Furthermore, the paper finds a spatial decay effect in walking access distance, the decay rate of which, however, varies across stations. Terminal stations have a larger pedestrian catchment area than in regular and exchange stations. Moreover, the passengers of Nanjing Metro Line 2 can be classified into six groups according to their demographic characteristics, among which education and occupation are vital indicators in determining their willingness to walk to the stations. Middle-class passengers have a higher dependence on the metro and tend to walk longer than other groups do. This study provides an important reference for planners and transport sectors to optimize land-use and transport infrastructures.