To effectively link the consolidation and expansion of poverty alleviation achievements with rural revitalization, it is necessary to turn the experience of targeted poverty alleviation of enterprises into a new driving force for rural revitalization. The peer behavior widely existing in the practice of targeted poverty alleviation by enterprises has a multiplier effect. However, the existing literature on the peer effect of targeted poverty alleviation by enterprises is limited to the regional and industrial levels, which needs to be expanded and deepened. The board network formed by the same person serving as directors in different enterprises is a common phenomenon in China’s capital market. It has a strong information transmission function, which can broaden the information access channels and improve the quality of information acquisition, and generate the peer effect through the learning mechanism among enterprises, which in turn leads to the convergence of the behavior of peer enterprises. Based on the empirical analysis of Shanghai-Shenzhen A-share listed companies from 2016 to 2020, it is found that: (1) on the whole, the formation of a board network can promote the targeted poverty alleviation behavior of enterprises, which shows that the probability of participating in targeted poverty alleviation and the investment of poverty alleviation funds of enterprises with board networks are significantly higher than those without board network; (2) the peer effect of targeted poverty alleviation by enterprises under the role of board network is significant, which is reflected in the targeted poverty alleviation behavior (the probability of participating in targeted poverty alleviation and the investment of poverty alleviation funds) of target enterprises will be enhanced by the increase of targeted poverty alleviation behavior of the same group of enterprises. This peer effect is significant in different types of board networks and for different poverty alleviation methods; (3) the board network produces the peer effect of targeted poverty alleviation mainly through the information transmission mechanism and enterprise learning mechanism, which shows that the increase of the target enterprise’s structural hole positions and the number of board meetings will strengthen the peer effect; (4) the effect of targeted poverty alleviation by enterprises also has a certain peer effect, which shows that there is a significant positive correlation between the number of people helped out of poverty by target enterprises and the number of people helped out of poverty by peer enterprises; (5) the peer effect of targeted poverty alleviation will have good economic consequences on the development of enterprises, which is manifested in that the improvement of targeted poverty alleviation behavior brought by the peer effect is conducive to the improvement of enterprise value and the increase of government subsidies. Besides, in addition to the peer enterprises based on the board network, there is also a significant convergence phenomenon of targeted poverty alleviation behaviors among peer enterprises in the same region and industry. Based on the existing literature, this paper explores the peer effect of targeted poverty alleviation and its formation mechanism under the role of board networks, and conducts an empirical test. It has expanded and deepened the research on the economic effects of the board network and the empirical analysis of targeted poverty alleviation by enterprises, which is helpful to the consolidation and expansion of poverty alleviation achievements and the effective connection with rural revitalization. This study shows that the peer effect of targeted poverty alleviation by enterprises is widespread and has a positive multiplier effect. In the process of consolidating and expanding the achievements of poverty alleviation and effectively connecting with rural revitalization, on the one hand, the government should encourage enterprises to actively participate in rural revitalization and provide reasonable guidance; on the other hand, enterprises should strengthen information communication and mutual learning, make full use of the multi-dimensional peer effect, and actively participate in the practice of comprehensively promoting rural revitalization, so as to achieve a win-win situation between enterprise development and social progress.