BACKGROUND: The built and social environments may contribute to physical activity motivations and behavior. We examined the extent to which the Theory of Planned Behavior (TPB) mediated the association between neighborhood walkability and walking. METHODS: Two random cross-sectional samples (n = 4422 adults) completed telephone interviews capturing walking-related TPB variables (perceived behavioral control (PBC), attitudes, subjective norm, intention). Of those, 2006 completed a self-administered questionnaire capturing walkability, social support (friends, family, dog ownership), and neighborhood-based transportation (NTW) and recreational walking (NRW). The likelihood of undertaking 1) any vs. none and 2) sufficient vs. insufficient levels (≥150 vs. <150 minutes/week) of NTW and NWR, in relation to walkability, social support, and TPB was estimated. RESULTS: Any and sufficient NTW were associated with access to services, connectivity, residential density, not owning a dog (any NTW only), and friend and family support. Any and sufficient NRW were associated with neighborhood aesthetics (any NRW only), dog ownership, and friend and family support. PBC partially mediated the association between access to services and NTW (any and sufficient), while experiential attitudes partially mediated the association between neighborhood aesthetics and any NRW. CONCLUSIONS: Interventions that increase positive perceptions of the built environment may motivate adults to undertake more walking.