High-tech industrial agglomeration is conducive to boosting technological progress, promoting industrial structure upgrading and realizing economic transformation, and certainly affects the overall industrial environmental efficiency. However, few recent studies have focused on its impact on industrial environmental efficiency from a green perspective. In the context of promoting the development of green economy, it is of great significance to clarify the links between high-tech industrial agglomeration and industrial environmental efficiency. In this research, we first analyzed the theoretical mechanism of the impact of high-tech industrial agglomeration and its spatial spillover effects on industrial environmental efficiency and then made an empirical analysis based on the panel data of 29 provinces and cities in China from 2003 to 2016. During the research, Super-DEA method, ESDA method and spatial Dubin model are used. The result shows that: (1) There is a significant spatial positive correlation between China's industrial environmental efficiency and high-tech industrial agglomeration; (2) high-tech industrial agglomeration has improved the local industrial productivity and industrial technology level through scale effects and technical effects, which has accordingly significantly enhanced the corresponding environmental efficiency; (3) through the association of regional industries, the cross-regional cooperation of enterprises and the formation of innovation networks, high-tech industrial agglomeration promotes the spillover of knowledge and technology among regions, improves the level of industrial technology in neighboring regions, and enhances the industrial environmental efficiency in neighboring regions. All these three is helpful to re-evaluate the development mode of high-tech industry agglomeration and to formulate relevant government policies.