In recent years, China’s overseas investment has accelerated, and private enterprises have become an indispensable force in the wave of overseas investment and are playing an increasingly important role. However, in the complex and changeable world economy, private enterprises are faced to both internal and external challenges in the process of overseas investment. In this context, this paper employs Chinese Private Enterprises Survey (CPES) database during the period of 1993~2012 to examine the effects of political connection, educational background and professional background on private enterprises’decision-making in overseas investment. In the theoretical analysis, this paper suggest that political connection can bring information effect, resource effect and protection effect to enterprises, thereby promoting enterprises to make and implement scientific and high-quality overseas investment decisions. In terms of educational background, a higher level of education can improve entrepreneurs’ability in cognition and dealing with complex problems, and overseas study experience can bring information and resource advantages to enterprises, which contributes to the implementation of overseas investment decisions of enterprises. In terms of professional background, the entrepreneurs with professional experiences of technology, production, marketing and management can rely on their personal knowledge, market perception ability and organizational coordination ability to improve the comprehensive capability of the enterprises, thereby stimulating the overseas investment decision-making of the enterprises. The empirical results show that these three heterogeneous characteristics of private entrepreneurs, including political connection, educational background and professional background, generate significantly positive impacts on enterprises’ overseas investment decision-making, which is consistent with the theoretical analysis. Based on the conclusion, this paper puts forward relevant policy recommendations for improving the business environment for overseas investment of private enterprises and promoting high-quality development of the private economy in China.