This study examines the influence of internationalization on corporate philanthropy, and further investigates the moderating effect of political participation of CEO (Chief Executive Officer). Using a sample of Chinese family firms and hand-collected data on corporate philanthropy, internationalization, and CEO’s political participation, our findings show that internationalization is significantly positively associated with corporate philanthropy, suggesting that internationalization plays an important role in promoting corporate philanthropy because of the mounting interaction of corporate philanthropic consciousness among multinational companies. In addition, CEO’s political participation reinforces the positive association between internationalization and corporate philanthropy. Above findings are robust to a variety of sensitivity tests and further our conclusions are still valid after controlling for the endogeneity between internationalization and corporate philanthropy.