A novel approach, based on Species sensitivity distribution (SSD), is proposed for the development of an index for classifying ecotoxicological pesticide risk in surface waters. In this approach, the concept of TER (Toxicity Exposure Ratio), commonly used in traditional risk indices, is substituted by the concept of PAF (Potentially Affected Fraction), which takes into account several species within the biological community of interest, rather than just a small number of indicator species assumed as being representative of the ecosystem. The procedure represents a probabilistic tool to quantitatively assess the ecotoxicological risk on biodiversity considering the distribution of toxicological sensitivity. It can be applied to assess chemical risk on generic aquatic and terrestrial communities as well as on site-specific natural communities. Examples of its application are shown for some pesticides in freshwater ecosystems. In order to overcome the problem of insufficient reliable ecotoxicological data, a methodology and related algorithms are proposed for predicting SSD curves for chemicals that do not have sufficient available data. The methodology is applicable within congeneric classes of chemicals and has been tested and statistically validated on a group of organophosphorus insecticides. Values and limitations of the approach are discussed.