The debate on pedestrian-friendly urban structures has increased interest in the connections among land use, accessibility, and pedestrian volume. Most econometric models have focused on the individual and separate effects of density, land-use patterns, and street connectivity on the spatial variation of walking. This study investigates the effects of spatial accessibility and centrality by land-use types on pedestrian presence in Seoul in 2009. The model employs four newly developed accessibility indices and identifies the differentiated effects of land-use accessibility and centrality on pedestrian volume, controlling for street features, location and transportation characteristics, and neighborhood land-use attributes. The model results confirm that the effects of land-use accessibility and centrality vary with the spatial distribution of pedestrians. This analysis highlights the importance of investigating accessibility effects by land-use volume. Indeed, policies on pedestrian-friendly urban structures should consider local contexts as well as the complex relationship between land-use accessibility and walking.