It is one of the important enlightenments of 40 years' development of China's scientific and technological innovation reform to strengthen the main position of enterprises in technological innovation and give full play to the main role of enterprises in the technological innovation system. It integrates the concept of enterprise technological innovation elements, process and performance, puts forward the process model of enterprise technological innovation from the perspective of NIS, and establishes the EKV evaluation framework and index system of enterprise technological innovation subject status, The comprehensive index method is used to synthesize the evaluation index of technological innovation subject status of enterprises in Guizhou Province. The results show that since the 11th five year plan, the technological innovation subject status of enterprises in Guizhou Province has been greatly improved. The TSI index has increased from 58.35% in 2006 to 80.54% in 2018. As a western province, the gap between technological innovation ability of enterprises in Guizhou Province and the whole country has narrowed from 41.65% to 19.46%, among which the enterprise innovation factors are integrated The gap between synergy, innovation knowledge reengineering and innovation value realization of enterprises and the national level has been reduced to 3.92%, 19.5% ,34.96% respectively. Through the research on the contribution rate and sensitivity of evaluation indexes at all levels, the important indexes and key sensitive indexes for improving the technological innovation ability of enterprises in Guizhou Province have been found out, and several policy suggestions have been put forward accordingly