Current evidence on neighborhood walkability and active commuting focuses on residential rather than workplace environment. This cross-sectional study investigated whether higher workplace walkability (WW) was associated with commute walking, both independently and together with residential walkability, using data from 6769 respondents of the 2017 Dutch national travel survey. In a fully adjusted logistic regression model, 10% increase in WW was associated with 32% higher odds of commute walking (Odds ratio (OR): 1.31, 95% Confidence Interval (CI: 1.27–1.36). The estimates were stronger in rural dwellers than urban residents, (ORrural 1.49, 95%CI: 1.34–1.64 vs ORhighly.urban 1.19, 95%CI: 1.13–1.26). In participants with both high residential walkability and WW, we observed 215% higher odds (OR 3.15, 95% CI: 2.48–3.99) of commute walking compared to those with low walkability in both. Our study indicated the importance and complementary nature of walkable residence and workplace in contribution to physical activity of working individuals through active commuting.