Despite numerous evidence for the leader's role in facilitating employees' green behavior, few studies have delved into the intervening mechanisms of the trickle‐down effect transmitting green behavior from leaders to their subordinates. Drawing on social learning theory, we explicate a trickle‐down process for voluntary green behavior from leaders to subordinates through leaders' green role model influence and employees' green self‐efficacy, with leader gender as a moderator. Analysis of 70 leaders and 190 employees revealed that leaders' green role model influence and employees' green self‐efficacy sequentially mediated the relationship between voluntary green behavior of leaders and that of employees. Moreover, both the direct and indirect effects were moderated by leader gender: While the direct effect was stronger for male leaders, the sequential mediating effect was stronger for female leaders. Overall, our study confirms the utility of social learning theory in explaining the trickle‐down effect of voluntary green behavior at work.