In collaborative innovation, personal relationships between boundary personnel of knowledge-intensive business service (KIBS) enterprises and organizational customers have a “double-edged sword” effect on inter-organizational relations. This study adopts the empirical research method based on KIBS enterprises’ cooperative innovation projects with organizational customers in China. Based on the theory of the inter-organizational relationship, this study explores the influence of personal relationships between employees at the boundary of enterprises on organizational customers’ opportunistic behavior. It analyzes the mediating effect of relationship governance and contract governance. The results show that personal relationships between boundary personnel will improve the probability of corporate customer opportunism. The relationship between governance and contract governance for enterprises can effectively restrain the opportunistic behavior of organizational customers. Further, the personal relationships between boundary personnel will enhance the relationship norms and inhibit the opportunistic behavior of organizational customers, and relationship governance plays a partial intermediary role in this. The personal relationships between employees at an enterprise’s boundary will relax the contract’s supervision and encourage corporate customer opportunism. Contract governance plays a partial intermediary role in this.