Motor vehicle exhaust emissions have made air pollution increasingly serious in China, and advocating for the concept of green travel can help alleviate the air pollution caused by motor vehicle exhaust. Thus, the research on the green travel choice behavior of limited rational individuals in the complex social network and the evolution of group behavior is the focus of this paper. Based on the theory of planned behavior, this paper established the individual cognition-behavior model. Meanwhile, an interaction model of individuals in the network is constructed based on the DeGroot model and scale-free network. The simulation results of the model show that: (1) it is difficult to control the behavior of green travel: even if the knowledge level of green travel is high, the proportion of green travel individuals in the group is still very low; (2) the individual intention for green travel is dependent on behavioral attitude, which can effectively improve the proportion of green travel individuals; (3) if the individual intention is too dependent on the subjective norm and the perception of behavioral result, the proportion of green travel individuals would become lower; and (4) when the network is connected, the proportion of individuals who choose green travel will reach the peak through social interaction and learning. This study has a certain practical significance for the environmental protection work of relevant departments, which can guide the behavior of individuals through the design of government institutions, and enable the concept of green travel to form an ideology by means of education and knowledge dissemination, so as to generate some kind of consensual behavioral consciousness. Meanwhile, this study provides a new research perspective for behavioral research and extends the research scope of group behavior.