To integrated the green development concept into the technological innovation activities of industrial enterprise has become a breakthrough to break the shackles of resources and environment, promoting sustainable development. This paper puts the energy consumption, such as "three wastes" emissions into the research framework, using the super network SBM model and Malmquist-Luenberger index to measure and evaluate industrial enterprises green technology innovation efficiency. The results showed that: In 2013-2018, industrial enterprises green technological innovation efficiency is relatively low. There are bigger differences between different provinces, but as time changes, provincial differences gradually narrow; The green technology innovation efficiency of China''s industrial enterprises presents a stepwise spatial distribution pattern of "east-middle-west" decreasing. Compared with the upward trend of green technology innovation efficiency of industrial enterprises in the eastern region, the efficiency level in the central and western regions not only has the characteristics of obviously low absolute level, but also shows differences in growth rates; The efficiency of achievements transformation period below the efficiency of science and technology research and development, pure technical efficiency is the main causes of green technology innovation low efficiency; The Malmquist-Luenberger index greater than 1,overall development situation is good, but the growth of technical efficiency change index is mainly depends on the pure technical efficiency. At the three regional levels, the ML index in the eastern region is mainly due to the growth of the technology progress index , while the ML index in the central and western regions is mainly dependent on the growth of the technological efficiency change index. Through the above research find out the real reasons of the green technology innovation low efficiency, give effective path for industrial enterprises to promote the green technology innovation.