Abstract: From the perspective of enterprise innovation value chain, the unexpected output is included in the research framework of technological innovation efficiency of iron and steel enterprises.The network SBM-DEA model and Malmquist index are used to study the green technological innovation efficiency and green total factor productivity of 12 iron and steel enterprises in China from 2011 to 2017.The results show that the efficiency of green technology innovation in iron and steel enterprises is moderate and showing an upward trend.The change trend of efficiency in different innovation sub-stages of iron and iron and steel enterprises is synchronous, but the efficiency values in different sub-stages are different.The transformation efficiency values of innovation achievements in most iron and steel enterprises are higher than those of R&D efficiency.The growth of green total factor productivity in iron and steel enterprises is mainly attributed to the progress of transformation efficiency of innovation achievements.Compared with the transformation stage of innovation achievements, the growth of green total factor productivity and its decomposition index in the R&D stage of science and technology is relatively weak.