In this study, we integrate work–family enrichment and upper echelons theories to examine how and when chief executive officers’ (CEOs’) family experiences impact their firms’ performance. We argue that CEO family harmony has an indirect effect on their firms’ product innovation performance through top management team (TMT) behavioral integration. Additionally, we propose that CEO founder status strengthens the effects of CEO family harmony. Our analysis of data from 101 CEOs and 458 TMT members in various high-tech industries in China indicates that the positive relationship between CEO family harmony and firms’ product innovation performance is mediated by TMT behavioral integration. Moreover, CEO founder status increases the direct effect of CEO family harmony on TMT behavioral integration and its indirect effect on firms’ product innovation performance through TMT behavioral integration. These findings have theoretical and practical implications and provide new research directions in the study of CEO family–work spillover and CEO–TMT interfaces.