This paper investigates the modal shift patterns of e-bike users in the Dutch context. We focus on the change in e-bikers’ travel behavior to assess whether this change benefits sustainability. Our study provides direct ecologically valid evidence on modal shift by using a longitudinal dataset from the Netherlands Mobility Panel survey. We examine e-bikers’ modal shift patterns before and after acquiring an e-bike. The findings indicate that after e-bike adoptions, conventional bike use reduces significantly, while car use reduces less strongly. Nonetheless, the share of car kilometers is much larger than that of conventional bikes at the baseline. Besides, the emission rate per passenger kilometer of an e-bike is several times lower than that of a car. These imply a net environmental gain after e-bike adoptions. The present study also sheds light on modal shifts at a disaggregated level by investigating those e-bikers who are more likely to drive less after e-bike adoption. The findings suggest that e-bikers younger than 50 and those around retirement age (60–69) seem more likely to step out of their cars. Additionally, people living in rural areas tend to be more likely to reduce their car use than their counterparts in highly urbanized areas. Based on our findings, we present policy recommendations for achieving a greener shift in mobility systems.