Urban residents’ perception of recycled water reuse is the foundation for the realization of recycled water reuse behavior. However, even though the perception factor is equipped, it does not mean that urban residents will use recycled water continuously for sure. Therefore, in this research, the authors try to put cognitive factors and emotional factors into a unified behavioral process. Based on this theory framework, the paper will interpret the initiation, formation and continuing process of recycled water reuse behavior of urban residents. On the basis of previous studies, this study established a theoretical model to study the influence of cognitive factors and emotional factors on recycled water reuse behavior of the residents. Based on the data of 325 samples, the direct and indirect relationship between the variables in the model is verified through path analysis and mediation analysis. The empirical results show that: firstly, the urban residents’ perception of recycled water reuse can activate their emotion for recycled water, and the emotion includes both positive emotion and negative emotion; secondly, although the recognition of recycled water can stimulate both positive and negative emotional factors, there are great differences between positive and negative emotions on the initiation, formation and sustainability of recycled water behavior. Negative emotion has a certain effect on the initiation of recycled water reuse behavior, but it has no significant effect on the formation and sustainability of recycled water reuse behavior. By contrast, positive emotion has no significant effect on the initiation of recycled water reuse behavior, but it has a significant effect on the formation and sustainability of recycled water reuse behavior. That is to say, at different stages, the recycled water reuse behaviors are affected differently by positive emotions and negative emotions. Thirdly, compared with negative emotional variables, positive emotions have a greater impact on individual recycled water reuse behavior. Positive emotional variables can significantly mediate the impact of cognitive variables on recycled water reuse behavior habits. In other words, positive emotions play a vital role in the sustainability of recycled water reuse.