Venture capital has very important influences on entrepreneurial firms' growth. Then, what would be the impact of venture capital on firms' internationalization? Based on RBV, agent theory, and signal transition theory, this paper analyzes the mechanism of the effect of venture capital on the internationalization of entrepreneurial firms, and the relation between characteristics of venture capital institutions and the internationalization of entrepreneurial firms, and empirically tests the hypotheses by unbalanced panel data from China's 300 listed high-tech companies. It comes to the results as follows:firstly, the involvement of venture capital not only improves the breadth of firms' internationalization, but also strengthens the depth of internationalization; secondly, the characteristics of venture capital institutions have different influences on entrepreneurial firms' internationalization, and entrepreneurial firms with foreign venture capital, venture capital with high industrial expertise, and syndication venture capital, have the advantages of broadening the breadth of the internationalization of entrepreneurial firms and promoting deep roots of entrepreneurial firms in international market. This paper not only extends existing firm internationalization theory, but also has reference for internationalization practice of entrepreneurial firms.