Prior studies grounded in the categorization-elaboration model (CEM) have shown that gender diversity has negative, positive, or mixed effects on the outcomes of units. By integrating the CEM, resource complementarity, and human capital resource perspectives, we investigate whether the founder CEO’s human capital resources can change the effect of workforce gender diversity as an untapped strategic resource on venture firm performance. We mainly focus on the context of knowledge- and technology-intensive venture firms and suggest that workforce gender diversity and the CEO’s human capital resources can jointly influence on venture firm performance. To consider the different functional effects of the founder CEO’s human capital resources, we categorize the resources into three types of prior work-related experience: entrepreneurial experience, human resource (HR) management experience, and same-industry experience. In an analysis of 1,413 venture firms, we find that gender diversity has a non-significant effect on venture firm performance but the founder CEO’s entrepreneurial experience has a functional effect on the relationship between gender diversity and venture firm performance. We also find that the functional effect is stronger when venture firms are in the rapid growth stage. Our findings indicate that the founder CEO’s human capital resources have a functional effect on the impact of gender diversity. This important finding contributes to the diversity and strategic human capital resource literature.