The question of whether appropriate decentralization can solve Corporate Social Responsibility (CSR) misplacement caused by Entrepreneurial Characteristics (EC) is an interesting ethical puzzle. Because corporate behavior depends on the decision-making choices of executives whose personality characteristics affect the choice tendency, power distribution undoubtedly becomes a big boost for most businesses to work out the adverse externality problems. Based on Upper Echelons Theory, this study developed a comparative impact model linking the effects of entrepreneurial intrinsic nature and experience characteristics on CSR performance. We tested the effective mechanism with the mediator role of the Corporate Power Distribution Index (CPDI) through a sample of listed Chinese companies from 2009 to 2017. The results provide that EC, such as female Gender, Degree, and Salary, have positive effects on CSR; CPDI plays a mediator role in the relationship between EC and CSR; and is moderated by Age, Academy, and Shares. The conclusion shows that EC can improve CSR performance to optimize CPDI to reduce corporate misplacement behavior.