Establishing a river chief system is stipulated in the newly amended Law of the People’s Republic of China on Prevention and Control of Water Pollution, which clarifies the liability of party or administrative heads at various levels for water environment rehabilitation in their own administrative regions. In this article, we analyze the implementation effects of the river chief in China, current assessment methods, and their deficiencies, and propose two quantitative assessing methods: (1) comprehensive water quality assessment for the cross sections of rivers and lakes and (2) assessment using the pollutant load intercepting rate of sewer networks, aiming to improve the scientific rationality for effect assessment of the river chief system. With Suzhou Creek rehabilitation in Shanghai as an example, application of the comprehensive water quality assessment method was introduced. By analyzing the pollutant load intercepting rate in various provinces (autonomous regions or municipalities) in China, we find that on average 34% wastewater is still discharged into water courses in an untreated state, leading to repeated occurrence of water quality deterioration. Introducing the comprehensive water quality assessment and the pollutant load intercepting rate into the river chief assessment will effectively push the government at all levels to concentrate their human, material, and financial resources onto urban drainage network correction and the interception of pollution sources discharged into watercourses.