By introducing data from A-share listed companies from 2011 to 2022, this paper empirically analyzes the impact of the improvement of new quality productivity on the binary margin of outward foreign direct investment (OFDI) of enterprises. The results show that new quality productivity can significantly improve the binary margin of OFDI of enterprises, and this conclusion still holds after a series of robustness tests and endogeneity treatments. Mechanism testing shows that new quality productivity enhances the binary margin of OFDI of enterprises by relaxing financing constraints, improving ESG performance, and increasing innovation output. Heterogeneity analysis shows that the impact of new quality productivity on the binary margin of OFDI is more pronounced in non-state-owned enterprises, non-heavy polluting enterprises, and non-high-tech enterprises, while the impact of new quality productivity on the intensive margin of OFDI is more pronounced in technology intensive and labor-intensive enterprises, and the impact on the extended margin is more pronounced in asset intensive enterprises. Expansion analysis shows that executives with overseas backgrounds play a positively regulatory role in the process of promoting the dual marginal effect of new quality productivity on enterprises’ OFDI. At the same time, new quality productivity also increases the probability of enterprises’ OFDI and overseas market profitability. The above research has first confirmed the positive impact of new quality productivity on enterprises’ OFDI, which not only enriches the existing international investment and productivity theories, but also provides theoretical guidance and useful references for the international development of China’s enterprises and the high-quality development of the China’s economy.