This paper proposes a risk assessment methodology for evaluating the surface water quality of hydrological basins based on physico-chemical parameter concentrations. Considering the Douro River basin in Portugal and monthly recorded dissolved oxygen and conductivity parameter measurements in 18 water sampling stations from January 2002 to December 2013, the work intends to answer the research question of identifying the riskiest periods for water pollution in the year and classifying the water sampling stations in terms of risk for water pollution. The methodology consists first in determining the pollution risk implied by the physico-chemical parameters, based on the monthly water station measurements, using six different risk measures, namely mean, variance, loss probability, entropy, mean excess loss and value at risk. The risk values are ordered according to each risk measure and a final ranking is established through a ranking aggregation method. The final ranking permitted identifying the high risk period as ranging from May to October and the low risk period from November to April. Furthermore, July was classified as riskiest month concerning the dissolved oxygen concentration, and August as riskiest month regarding the conductivity levels. On the other hand, the ranking allowed classifying the water sampling stations, previously grouped in clusters, in terms of similar risk for water pollution: six sampling stations in the west of the basin formed the riskiest cluster in the dry period considering the dissolved oxygen concentrations, and four of those stations formed also the riskiest cluster concerning the conductivity levels.