Inhibiting negative knowledge behavior is one of the ways to improve the effective circulation of knowledge within the organization. This study puts employees’ knowledge hiding behavior in the organizational relationship network situation and discusses the influence of network location on knowledge hiding, exploring the moderating role of knowledge acquisition in the relationship between network location and knowledge hiding. From the perspective of social network, 232 knowledge-based employees were used to obtain the data, and we used literature analysis, social network analysis, multiple regression analysis, UCINET, SPSS, and other software packages. Research shows that employees in the central network are less willing to do knowledge hiding behavior, and those in the structural hole network tend to do knowledge hiding behavior. Knowledge acquisition as the supply way of knowledge resources plays a positive role on the negative relationship between centrality and knowledge hiding and on the positive relationship between structure hole and knowledge hiding. The research results have positive significance for understanding and mastering the hiding behavior law of individual knowledge in the organizational relationship network and also provide certain theoretical basis and data support for organizational knowledge governance.