Much of the established literature focuses on the impact of digital supply chain innovation on cost reduction, efficiency, and supply chain security but generally ignores whether digital supply chain innovation affects firm ESG (Environmental, Social, and Governance) performance. This paper constructs a quasi-natural experiment with the supply chain innovation and application pilot in China to explore the impact of digital supply chain innovation on firm ESG performance. The study analyzes data from China's A-share listed companies from 2012 to 2022, utilizing the PSM-DID method to conclude. The findings reveal that digital supply chain innovation enhances firm ESG performance by improving organizational synergy, green innovation, and firm governance. The study also indicates that the effect is more significant in samples with poorer supply chain operating environments, higher supply chain relationship tightness, and better firm management ability. Furthermore, the ESG governance effect of digital supply chain innovation increases the firm value and promotes sustainable development. However, it only significantly contributes to firm environmental (E) and governance (G) performance. The article provides preliminary micro-evidence from China on the ESG governance effects of digital supply chain innovation and provides important policy insights for further unleashing the construction effects of digital supply chain innovation to promote high-quality development.