To address endogeneity concerns stemming from firm‐CEO matching, the authors deploy a two‐sided matching model that identifies the complementarities arising from the CEO‐firm match and subsequently account for these complementarities in empirical tests. Applying this approach, they examine how the nature of CEOs’ human capital affects the acquisition behavior and performance of firms. The authors find that generalist CEOs (CEOs with a broader set of knowledge and skills) are more likely to engage in unrelated acquisitions than specialist CEOs (CEOs with a narrower but deeper set of knowledge and skills). they also find that the fit between the nature of CEOs’ human capital and the type of acquisitions they undertake is associated with stronger performance. The paper contributes to research on CEOs, human capital, M&As, and microfoundations.