Our study purpose is to analyze the tobacco industry’s sustainable practices by investigating how and when green human resources management (GHRM) practices influence the development of the organizational citizenship behavior for the environment (OCBE) at the individual level. Therefore, we focus on OCBE as a mediation mechanism (how) and green culture enablers as a serial mediation (when) for the nexuses between GRHM, OCBE, and organizational performance (OP). The employee behavior requires the support of managers (leadership), who serve as enablers to ensure long-term goals and increase organizational resources. Data from 410 respondents in the tobacco industry in Pakistan were analyzed using descriptive analysis, confirmatory factor analysis, and the PLS-SEM model. Our results proved that GHRM significantly increased OP. In practice, our findings are helpful for managers as guidelines for the decision-making process related to improving the organizational culture and employee green behavior to improve sustainability in the tobacco industry.