Residents' participation in pro-environment behaviors (PEBs), as an indispensable part of solving urban environmental problems, is important for cities to promote sustainable development. Place attachment (PA) could play a pivotal role in encouraging residents' PEBs, yet the conclusions are inconsistent. The present study explores the research gaps on how place attachment affects residents' decision-making of engaging in PEBs. This study employs a combined approach of survey and experimental studies, and integrates empathy with nature and nature relatedness to gain a deeper comprehension of the underlying mechanisms. In Study 1, using large-scale data collected in Beijing (n = 1,128), we found that place attachment was positively correlated with PEBs through the role of empathy with nature and nature relatedness. To further examine the causal link, we manipulated place attachment using a scenario simulation approach in Study 2 (n = 230). Our results demonstrate the robust causal link between place attachment and PEBs. In addition, we further validated the sequential mediating role of both empathy with nature and nature relatedness in this relationship. This study opens new avenues for local government to improve environmental management. The findings are further explored in terms of both theoretical and practical implications.