The analysis of river pollution and assessment of spatial and temporal variation in hydrochemistry are essential to river water pollution control in the context of rapid economic growth and growing pollution threats in China. In this study, we focused on hydrochemical characteristics of the Luanhe River Basin (China) and evaluation of 12 hydrochemical variables obtained from 32 monitoring stations during 2001–2010. In each study year, the streams were monitored in the three hydrological periods (April, August, and October) to observe differences in the impacts of agricultural activity and rainfall pattern. Multivariate statistical methods were applied to the data set, and the river water hydrochemical characteristics were assessed using the water quality identification index (WQIIM). The results showed that parameters had variable contribution to water quality status in different months except for ammonia nitrogen (NH4-N) and total nitrogen (TN), which were the most important parameters in contributing to water quality variations for all three periods. Results of WQIIM revealed that 18 sites were classified as 'meeting standard' while the other 14 sites were classified as 'not meeting standard', with most of the seriously polluted sites located in urban area, mainly due to discharge of wastewater from domestic and industrial sources. Sites with low pollution level were located primarily in smaller tributaries, whereas sites of medium and high pollution levels were in the main river channel and the larger tributaries. Our findings provide valuable information and guidance for water pollution control and water resource management in the Luanhe River Basin.