New ventures often innovate by building on the technology of incumbent firms. The resulting technological links that form between new ventures and incumbents can open up valuable collaborative opportunities between them. Nonetheless, because these technological links also increase incumbents’ abilities to misappropriate the knowledge of new ventures, such collaboration can render new ventures particularly susceptible to the opportunistic whims of their incumbent partners. Whether technological links promote or impede corporate venture capital (CVC) deal formation may depend on incumbent firms’ propensities to behave opportunistically and how aware new ventures are of such propensities. We argue that when new ventures have social ties to incumbent firms that have opportunistic tendencies, technological links between them strongly impede CVC deal formation. In such cases, social ties substantiate new ventures’ fears of knowledge misappropriation that might occur. In contrast, when new ventures have social ties to incumbent firms that lack opportunistic tendencies, technological links between them strongly promote CVC deal formation as social ties validate the incumbent firm’s trustworthiness and the potential for productive collaboration as a result of technological links. Using a data set that integrates patent citations, hand-collected career histories, and infringement lawsuits, we tracked the investment pattern between 29 incumbents and 402 new ventures in the U.S. information technology industry and found support for our arguments.