This paper contributes to our understanding of how to improve manufacturing firms' green operations underpinned by the proactive behavior theory. Chinese manufacturing firms are focused on because of their significant impact on global climate change and distinctive governance structure. Specifically, we survey 155 highest-level environmental managers (EMs) in these firms who have an ultimate decision-making power on environmental issues, and investigate the antecedents and consequence of their proactive pollution reduction behavior (PPRB). Through identifying the psychological motivation implied in EMs' environmental management behavior, we find that both EMs' role breadth self-efficacy (including in-role self-efficacy and extra-role self-efficacy) and felt responsibility (including felt responsibility establishment and felt responsibility coordination) can improve their PPRB. Further, available resources in firms only positively moderate the impact of extra-role self-efficacy on PPRB, and incentives from external stakeholders only moderate the impact of felt responsibility establishment on PPRB. Our empirical results also confirm that PPRB can improve corporate operational performance, strategic competitiveness, and environmental performance, but a higher level of PPRB's performance comes more from the driving force of PPRB's antecedents rather than PPRB itself.