Residents’ environmental citizenship behavior is essential to the environmental protection and sustainable development of rural destinations. However, previous research with regards to environmental citizenship behavior has focused on an employee perspective, rather than a resident one. Through the theoretical lens of the Stimulus-Organism-Response (SOR) model, our research examined how perceived environmental CSR (ECSR) contributes to residents’ environmental citizenship behavior, with resident-environment relationship quality acting as the organism. Data collected from a Chinese rural destination were analyzed with a structural equation modeling approach. Results indicate that: (1) perceived ECSR directly and positively influences residents’ environmental citizenship behavior; (2) relationship quality variables (i.e., environmental identification and environmental commitment) directly and positively affect residents’ environmental citizenship behavior; (3) environmental identification directly and positively affects environmental commitment; (4) relationship quality variables positively mediate the effect of perceived ECSR on residents’ environmental citizenship behavior. The current research complements existing tourism literature on environmental citizenship behavior with a focus on perceived ECSR and relationship quality from the aspect of residents in rural destinations. The findings also provide some practical implications that potentially facilitate the adoption of environmental citizenship behavior among residents for sustainable destination management.