<p>Adverse rulings in the raw materials and rare earths cases have made it necessary for governments to establish a more compliance-oriented, tariff-alternative policy framework. Existing research has predominantly focused on the rare earths sector, while insufficient scholarly attention has been paid to analyzing the evolutionary mechanisms of tungsten resource policies and evaluating the effectiveness of their corresponding substitution policies. Second, although quasi-natural experimental methods (for example, the synthetic control method (SCM) and difference-in-differences (DID)) have demonstrated robust advantages in policy evaluation, their application remains unexplored in this field. Focusing on tungsten resources, this study systematically investigates the evolutionary trajectory of policy frameworks and pioneers the application of quasi-natural experimental methods to evaluate the implementation efficacy of tariff substitution policies. We first review the evolution of China’s tungsten policies and divide them into three phases: the exploration and transformation phase, the restriction and promotion phase, and the protection and limitation phase. To further investigate the implementation effects of China’s tungsten industry policies, we establish time series models, SCM, and DID models to test the effects of different phases of China’s tungsten industry policies, tungsten export tariff policy, and the ad valorem resource tax reform. The conclusions are as follows: Tungsten industry policies during the restriction and promotion phase significantly increase export volume, export value, and environmental pollution, while the policies during the protection and limitation phase significantly reduce these indicators. However, the staged policies do not have a clear effect on tungsten prices. The tungsten export tariff policy reduced export volume but had no significant impact on export value or export price. The ad valorem resource tax reform effectively increased the price of tungsten resources and export revenue, while also reducing the export volume. To protect and efficiently use tungsten resources, China should support and encourage enterprises to engage in the deep processing of tungsten products, strengthen environmental regulation and green development support, enhance the guiding role of the resource tax based on value, and implement dynamic regulatory policies to flexibly respond to market changes.</p>