Environmental enterprise systems (EES) are an emerging type of integrated enterprise-grade software developed for environmental sustainability. This paper reports an exploratory investigation into the use and value of EES based on case studies of an EES vendor, four organisations that have adopted EES and an organisation that has yet to adopt EES in Australia. Two levels of EES usage are found: basic and advanced (in a relative sense). The basic level spurs the development of EES best practice and systemic competence in terms of environmental data capture, integrated energy, waste, emission and water database and ability to generate different reports with ease and high level of quality, thereby leading to environmental operational value. The advanced level, however, goes beyond basic EES affordances, to create EES-enabled distinctive capabilities such as innovation in terms of energy optimisation of assets, risk management and analytics for achieving environmental strategic value. Based on the findings, this paper highlights a pathway for harvesting environmental value from EES without affecting the economic aspect of an organisation.