Recent literature in the domain of environmental management suggests that employees' behavior is vital to enhance environmental performance. Despite this, little effort has been made to study how human resource management is linked with the environmental performance. Even less attention has been given to a joint consideration of green innovation and green human resources management and their contribution to environmental performance. The purpose of the current study is to investigate the interrelationship between green high performance work system (GPWS) and environmental performance through the mediation of green ambidexterity. A variance‐based structural equation modeling (partial least squares) was applied to a sample of Spanish hotel firms. The results indicate that GHPWS facilitate the development of green ambidexterity, and that this variable contributes to improved environmental performance. The results of this study make several contributions to the GHRM and green ambidexterity literature, as well as practical contributions for managers.