The era of the Internet has broadened the channels for citizens to participate in environmental governance, providing favorable conditions for observing the relationship between subjective perceptions of government performance and public participation. Does the public’s perception of government performance in black-odor waters governance affect their environmental participation? And through which channels and mechanisms of action does the perception of government performance in governance have an impact? This article empirically examines these questions based on 412 valid field questionnaires and 1202 online hotline inquiries. It is found that the perception of government environmental governance performance significantly increases the probability of citizens’ environmental participation, in which individual norms play a mediating role. Under the framework of the original theory of planned behavior, this paper introduces two emotional component variables, pollution perception and political trust, for residents. It is found that groups with strong pollution perceptions are more reluctant to participate in black-odor waters treatment, and good perceptions of government governance performance can effectively mitigate this negative effect. Political trust, on the other hand, mainly constrains individual public norms by way of constructing intrinsic constraints to increase the probability of environmental participation among pro-environmentalist groups. The benchmarking results are also re-evaluated using online appeal texts. The empirical results of this paper provide empirical evidence on how to introduce psychological tools in public management practice to improve public environmental participation behavior.