Ecological poverty alleviation launched by the Chinese government is an innovative green development measure that combines targeted poverty alleviation with ecological protection to realize the ecological environmental protection and income growth of the impoverished population. Based on the Chinese government’s policy of poverty alleviation assessment for provincial government officials in 2016, this paper studies whether the assessment of government officials promote enterprises’ participation in ecological poverty alleviation. Using the sample of Chinese A-share listed companies from 2016 to 2020, the empirical test shows that the more important the assessment of poverty alleviation by officials, the more likely local enterprises are to participate in targeted poverty alleviation and the higher the investment level is likely to be. The results pass a series of robustness tests. In addition, this paper further finds that enterprise participation in ecological poverty alleviation can effectively reduce local water pollution, air pollution and solid pollution, thus improving the ecological environment. It suggests that the assessment mechanism of Chinese government officials can effectively promote multi-dimensional ecological poverty alleviation. The contributions of this paper are as follows. Firstly, it is helpful to expand the relevant literature on enterprise environmental protection from the perspective of ecological poverty alleviation. Secondly, it is helpful to expand the literature related to government–enterprise interaction from the perspective of the assessment of government officials. Finally, it is helpful to enrich and expand the relevant literatures on promotion incentives of government officials from the perspective of ecological poverty alleviation.