Employing resource-based perspectives of the firm as a theoretical foundation, this article empirically examines the relationship between women in two different types of leadership roles and environmentally sustainable firms. I study an unbalanced panel data set of 2,006 wine firms in Australia for the period 2007–2014. The results suggests that when accounting for their individual, independent effects, women in technical leadership roles are positively associated with environmental sustainability, while women in professional leadership roles are not. However, the potential complementarities of women in both roles are explored, their interactive, co-joint (complementary) effect explains significantly more variance in the environmental sustainability variable than their individual effects. The results are discussed along with limitations and directions for future research.