People’s actions are always accompanied with multiple motives. How to estimate the role of the pro-environment motivation under the interference of other motivations will help us to better interpret human environmental behaviors. On the basis of classical motivation theories and travel mode choice research backgrounds, the concepts of pro-environmental and self-interested motivation were defined. Then based on survey data on 1244 urban residents in the Jiangsu Province in China, the multinomial logistic regression model was constructed to examine the effects of multiple motivations, government measures, and demographic characteristics on residents’ travel mode choice behaviors. The result indicates that compared to car use, pro-environmental motivation certainly has a significant and positive role in promoting green travel mode choices (walking, bicycling, and using public transport), but this unstable green behavior is always dominated by self-interested motivations rather than the pro-environmental motivation. In addition, the effects of gender, age, income, vehicle ownership, travel distance, and government instruments show significant differences among travel mode choices. The findings suggest that pro-environmental motivation needs to be stressed and highlighted to ensure sustainable urban transportation. However, policies aimed to only increase the public awareness of environment protection are not enough; tailored policy interventions should be targeted to specific groups having different main motivations.