The rapid development of China's economy and urbanization has led to the rapid deterioration of the ecological environment. This study aims to explore the relationship between provincial eco-efficiency and technological innovation in China. The DEA model is used to measure the ecological efficiency of 30 regions in China by using the data from 2007 to 2017, and different spatial econometric models were used to explore the influencing factors of ecological efficiency. The results show that in terms of ecological efficiency, the western region has the highest ecological efficiency, and the eastern region has the lowest. However, with the acceleration of urbanization, the ecological efficiency of the three regions gradually declined, and the last three regions basically remained at the same level. Based on spatial econometric analysis, the relationship between technological innovation and ecological efficiency is discussed. The results show that technological innovation has a negative impact on ecological efficiency, which confirms the existence of the environmental Kuznets Curve. In addition, environmental regulation and education level can improve ecological efficiency, while urbanization rate can reduce ecological efficiency. At the same time, spatial spillover effect plays an important role in technological innovation, environmental regulation, education level and urbanization rate in the change of regional ecological efficiency. Policy recommendations for further strengthening environmental protection and sustainable development are discussed.