After the industrial revolution, mankind experienced an unprecedented economic boom. However, what follows is a gradual environmental depredation and its consequences. The world has therefore paid much attention to environmental issues, and being green to protect Mother Earth has become a global movement. This study has distributed questionnaires to 522 teachers in the national elementary schools in Tainan City. It aims to explore the relations among the concerns over environmental issues, the behavioral intention to perform environmental protection, and the actual practice of environmental protection. Analyses of the findings show that elementary school teachers are most concerned about “Health and Safety” issues and are least concerned over “Ecological Protection”. Their concerns on environmental protection issues, behavioral intention to perform environmental protection, and practice of environmental protection are moderately positively correlated. The teachers’ environmental protection behavior may be effectively predicted based on their concerns on environmental issues and their behavioral intention to perform environmental protection. Structural equation modeling demonstrates that the theory fits the findings well. Multiple group analysis confirms the model stability and cross-gender validity. In the last section, relevant recommendations are provided for the reference of education authorities and future studies.