As one of the most important human resources of an enterprise, the CEO’s personal characteristics have an important impact on the productivity of the enterprise. Based on a sample of all A-share listed companies from 2008 to 2017, we find that CEOs with financial backgrounds are more adventurous and are more familiar with the financial sector’s operating practices, which can help companies to improve their level of innovation and investment efficiency, so they can help to increase the enterprise’s total factor productivity. The results remained significant after using the DID method to control the endogenous problem. Further, this influence is more pronounced in the enterprises where the CEOs have more personal influence such as low-profit enterprises and the enterprises which aren’t in the Beijing, Shanghai, Guangzhou and Shenzhen area. The conclusion of this paper corroborates the conclusion of “Upper Echelon” and “Imprinting” theory, and at the same time, it provides some new thinking for whether to hire the CEOs with financial backgrounds in the future. CEOs with financial backgrounds are more adventurous which will carry some risks for the enterprise, but also can play a role in improving the productivity level of the enterprise.