ABSTRACT Through the lens of organizational homophily, our study analyzes the network behavior of family firms in the high-risk context of family corporate venture capital (CVC). Specifically, we examine family corporate venture capitalists’ patterns in syndicate partner relationships using a global sample of 3,130 coinvestments from 2007 to 2022. We find that family corporate venture capitalists are more likely than their nonfamily counterparts to coinvest with syndicate partners who possess a similar wealth of experience in terms of overall investment experience, industry experience, and specialization. Family corporate venture capitalists follow the expected homophilic behavior of family firms when selecting nonfamily partners. This phenomenon is less pronounced in larger syndicates wherein individual syndicate partners may have less influence and there may be looser bonds between coinvestors. Our study contributes to research on family firms’ venturing and social capital as well as on CVC syndication.