To support the scientific policy making and planning for promoting the share rate of sustainable public transit in urban areas of large metropolises, this study analyzes the influences of psychological resistance to change factors on commuters’ mode shift behavior while some external changes happen in the transport supplies. The heterogeneities in the car users’ stickiness to car and the metro users’ loyalty to metro are examined to support individual-specific travel behavior prediction. Web-scripted efficient experimental stated preference surveys including four commuting modes and three key factors are generated, and face-to-face interviews are conducted to collect reliable behavioral data. A hybrid choice approach, simultaneously considering the latent variables and quantitative level-of-service variables of different options, is employed for analysis. The results indicate that psychological resistance to change factors (routine seeking, cognitive rigidity, and emotion reaction) have significant and substantial influences on car users’ inclination to previously used commuting mode (i.e., car) in mode shift behavior. Car users with stronger routine seeking, stronger cognitive rigidity, and less emotion reaction show more predilection to car. Car users’ income level, gender, marital status, commuting distance, commuting time, license type, and flexible work time are found to partially explain the heterogeneity in car stickiness. In-vehicle crowding of public transit is a much more crucial factor for attracting car users to shift to public transit as compared to cost and travel time. Metro users with stronger routine seeking and less emotion reaction present a stronger inclination to metro in mode shift behavior. The influences of psychological resistance to change factors on metro users’ mode shift behavior are comparatively smaller than the influences of these factors on car users’ behavior. Metro users’ age, education level, commuting distance, commuting time, occupation, and flexible work time are identified to be associated with predilections for metro.