Selecting knowledge chain as the research object， this paper explored the impact of relational governance on group members cooperation in the knowledge chain，structured relational governance system of knowledge chain which included relational behavior governance mechanisms， controlling relationship mechanism and relational incentives mechanism，and proposed the research hypothesis， study its impact on the performance of organizations. Combined with the questionnaire data， this paper used structural equation to test the related hypotheses in this article. The study show that：There is a positive impact among knowledge chain relational governance mechanism and organizational cooperation performance and inter-organizational knowledge flow. Knowledge flow as a partial mediator between the relational behavior of the knowledge chain governance mechanisms and knowledge chain organizations cooperative performance，in relation to control relationship mechanism，relational incentives mechanism and knowledge chain organizations cooperative performance plays an intermediary role entirely.