In the green marketing literature, environmentally sustainable practices (ESPs), green perceived value (GPV), as well as customer citizenship behavior (CCB) have not received significant attention, particularly in the hotel industry context. The current study aims to examine the effect of ESPs on CCB in a sample of five-star eco-friendly hotels in Egypt. Furthermore, it attempts to identify the potential mediating role of GPV in the relationship between ESPs and CCB and to examine the extent to which GPV directly affects CCB. To achieve the study aim, a self-administrated questionnaire was developed and directed to a convenience sample of five-star eco-friendly hotel guests. A structural equation model (SEM) was applied to 374 forms from guests of the surveyed hotels. The findings of the study reveal that ESPs significantly and positively affect GPV and CCB. The GPV has a positive and significant effect on CCB. The GPV partially mediates the relationship between ESPs and CCB. These findings emphasized that environmentally sustainable hotel properties are rewarded by customers in the form of CCBs (i.e., feedback, helping others, advocacy, and tolerance) directly and indirectly (through GPV). Upon this, some practical implications have been suggested to improve managers’ understanding in order to enable them to better manage their ESPs and to achieve positive and optimum outcomes.