In the new era of Chinese economy stepping toward high‐quality development, with the enhancement of the public environmental protection awareness and continuous improvement of technological innovation level, it is of great significance to study how technological innovation reduces water contamination against unofficial environmental regulations, which is also the primary task of construction of ecological civilization. The purpose of this paper is to study the contribution of technological innovation to water pollution intensity at different quantile levels and to test the nonlinear relationship between technological innovation and water pollution emission intensity under informal environmental pollution. On the basis of the provincial panel data of China from 2002 to 2018, the model of quantile and panel threshold was constructed to empirically analyze the structural mutation and threshold effects of technological innovation on the intensity of water pollution in China against the environment of informal environmental regulation. The study found that the marginal effects of technological innovation on the intensity of water pollution in China had undergone structural changes. Under different water pollution intensity, technological innovation can reduce pollution between 0.167% and 0.415%; with informal environmental regulation as the threshold variable, when the intensity of informal environmental regulation is less than the threshold value of 0.2168, technological innovation has a significant inhibitory effect on China's water pollution intensity, and when the intensity of informal environmental regulation exceeds the threshold value, the mitigation effect of technological innovation on China's water pollution intensity is more significant. The inhibition effect of technological innovation on water pollution emission intensity changed from 0.437 to 0.474. Therefore, when formulating environmental pollution policies, local governments should make rational use of informal environmental regulations and technological innovation, improve the informal environmental regulation system, and promote water pollution control with science and technology. [ABSTRACT FROM AUTHOR]