The establishment of Pilot Free Trade Pilot Zones (PFTZs) constitutes a pivotal platform for advancing the high-quality development of the “Belt and Road” initiative, exerting a significant influence on China’s export trade. Leveraging China’s customs database and A-share listed company data from 2007 to 2016, this study examines the impact and mechanisms of PFTZs on China’s export trade at the company-HS8 product-export destination country level. The empirical findings demonstrate that: (1) PFTZs significantly enhance China’s export trade volume, and this conclusion remains robust after a series of rigorous tests. (2) Mechanism analysis reveals that PFTZs foster the development of China’s export trade through industrial agglomeration and the digital transformation of enterprises. (3) Heterogeneity analysis indicates that PFTZs exhibit a more pronounced effect in promoting export trade for state-owned enterprises, larger firms, labor-intensive and technology-intensive industries, as well as non-OECD countries and low- to middle-income economies. (4) Extended analysis suggests that the establishment of PFTZs generates synergistic effects with National Big Data Comprehensive Demonstration Zones and National Independent Innovation Demonstration Zones. This study provides policy implications for how PFTZs can promote China’s export trade and achieve high-level opening-up.