In the context of the rising trend of anti-globalization, how to enable the upgrading of export industries in the construction of digital infrastructure is an important part of promoting the high-quality development of China’s economy and realizing Chinese path to modernization. Based on the Panel data of 285 cities in China from 2005 to 2013, and taking China’s 3G network construction as a quasi-natural experiment, the impact of digital infrastructure construction on the upgrading of China’s export industry is evaluated by using the double difference method. The conclusion indicates that: (1) digital infrastructure has effectively promoted the upgrading of China’s export industry. After conducting strict identification assumptions and robustness tests, the empirical results are still robust. (2) From the perspective of impact mechanism, the construction of digital infrastructure promotes the upgrading of export industries by improving innovation efficiency and resource allocation efficiency. (3) The construction of digital infrastructure has a more significant upgrading effect on export industries in cities with good initial technological level, high-level areas, and high government execution efficiency. The research conclusion of this article provides a path and policy reference for China’s export transformation and upgrading from the perspective of digital infrastructure construction.