The outward foreign direct investment (OFDI) of the enterprises needs the encouragement and guide of their mother country, and tax policy has direct effect on the motive and behavior of OFDI enterprises. Tax structure is determined by both tax policy and industrial structure. Based on spatial-temporal heterogeneity of China’s tax structure, empirical analysis shows that local tax structure has significant effect on regional OFDI stock, that there is significantly negative correlation between income tax ratio and OFDI stock, that other tax ratio is positively correlated with OFDI stock, that the correlation between turnover tax ratio and OFDI stock is positive but is not significant, and that the relationship between tax structure and OFDI stock is interactive causality. Regional industrial structure upgrading is significantly positively correlated with OFDI stock and can adjust the effect of tax structure on OFDI stock, which significantly strengthen the negative effect of income tax ratio but significantly weaken the positive effect of other tax ratio. Currently, the domestic main force to promote OFDI of China’s enterprises is not “tax evasion” but is industrial structure upgrading and other factors of resources and environment cost pressure. Therefore, industrial structure upgrading itself can boost OFDI of the enterprises but can inhibit OFDI by improving domestic business environment and mitigating the pressure of resources and environment and so on. Governments should enhance the guide of the OFDI, and realize the coordination between industrial structure upgrading and OFDI. China’s enterprises should accelerate openness and development, actively optimize resources allocation and integrate into global value chain through OFDI.