Numerous organizations have emphasized the importance of unlocking the strategic value from human capital resources by incorporating Chief Human Resource Officers (CHROs) or Chief People Officers (CPOs) into their top management teams. Despite this, the impact of such roles on firm performance has been insufficiently explored. This paper delves into the role of CHROs in effectively deploying human capital resources to cultivate competitive advantages. Employing the “alignment” perspectives from the literatures on both human capital resources (HCR) and top management teams (TMT), we posit that CHROs amplify organizational efficiency by aligning the strategic oversight typical of top management with the operational insight characteristic of HR department leadership. This alignment is critical in managing the complex, cross-hierarchical activities involved in human capital resources deployment. We hypothesize that the presence of CHROs will moderate the relationship between a firm’s human capital resource stocks and its performance, with this effect intensifying when the CHRO wields greater power within the top management team and possesses substantial personal HR-related expertise and experience. Our empirical analysis of publicly listed Chinese companies from the Shanghai and Shenzhen Stock Exchanges between 2003 and 2020 largely corroborates our hypotheses. The paper concludes by outlining the significant theoretical and practical implications of our findings, highlighting the strategic value of CHROs in contemporary organizational structures and performance.