Value perception is an important basis for behavior coordination in collaborative governance. Two variables, collaborative ability and relationship quality, were introduced to form the theoretical framework of “perceived-competency-relations-behavior”. A chain-mediated model was constructed to explore the mediating effects of collaborative ability, relationship quality, and their joint influence on the relationship between value perception and behavior coordination. The results show that: value perception can significantly enhance behavior coordination in atmospheric collaborative governance; collaborative ability and relationship quality respectively serve as a mediator between value perception and behavior coordination; collaborative ability and relationship quality jointly play a chain mediating role between value perception and behavior coordination. The conclusions enrich the research on the intrinsic mechanism of value perception affecting behavior coordination, and can provide a reference for decision-making in exploring behavior coordination paths.