How to balance the two major demands of economic growth and ecological protection and promote the green transformation of economic development has become an important challenge in China’s new stage of development. In the new era, fully strengthening the enterprise environmental responsibility system is the key to solving this difficult problem. This paper manually collects the enterprises mentioned in the government procurement list of energy-saving products and environmental label products, and selects the data of A-share listed companies from 2003 to 2023 as the sample. Referring to the practices of Chen Aizhen and Wang Chuang (2023), a quantitative framework is constructed from four dimensions: compliance, transparency, proactiveness, and risk control. Four evaluation systems, namely, environmental management system certification, environmental governance performance disclosure, environmental protection activities, and environmental protection incidents, are selected to conduct a systematic assessment of the environmental management effectiveness and sustainable development commitment of enterprises. Scores of enterprises under the evaluation criteria are calculated. To avoid the possible biases caused by subjective empowerment, this paper adopts the method of equal weight summing, that is, directly adding up the specific indicator scores under the four evaluation systems and taking the logarithm to obtain the comprehensive scores of corporate environmental responsibility. The research finds that: First, government green procurement can promote enterprises to actively fulfill their environmental responsibilities. After a series of robustness tests and endogeneity tests, consistent conclusions can still be drawn. Second, government green procurement mainly promotes environmental sustainability through two channels: enhancing the level of environmental investment and the capacity for green technological innovation, so as to encourage enterprises to actively fulfill their environmental responsibilities. Third, the incentive effect is more pronounced among non-state-owned enterprises, enterprises operating in regions with weaker environmental regulation, and those facing intense product market competition. Furthermore, enterprises that fulfill their environmental responsibilities exhibit significantly lower levels of future inefficient investment and achieve significantly higher market value. Compared with existing literature, this paper offers two main contributions: First, in terms of research content, it is the first to quantitatively analyze the impact of government green procurement on the fulfillment of corporate environmental responsibilities, filling the gap in the research on the impact of government actions on the environmental behaviors of micro enterprises. Secondly, in terms of research perspectives, the impact of government green procurement on enterprises’ fulfillment of environmental responsibilities is analyzed from two different perspectives: the level of environmental investment and the level of green technological innovation capabilities, thereby expanding the research on the economic consequences of government green procurement at the company level. his study holds both theoretical and practical significance. Theoretically, it elucidates how government green procurement can prompt enterprises to actively fulfill their environmental responsibilities by influencing their environmental protection investment levels and green technological innovation capabilities. This provides a reference for understanding the transmission path between government green procurement and the fulfillment of environmental responsibilities. Practically, it studies the differential impact of government green procurement on the fulfillment of environmental responsibilities by enterprises in terms of ownership, the intensity of environmental regulations, and the degree of competition in the product market. This is conducive to further improving the model of the government’s green procurement system and enhancing the cost-benefit balance in time and space for environmental governance.