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A wide range of Pharmaceuticals and Personal Care Products (PPCPs) are present in the environment, and many of their adverse effects are unknown. The environmental risk assessment (ERA) of twenty six PPCPs of high consumption and occurrence in Spain was done in this work. Based on ecotoxicity values obtained by bioluminescence and respirometry assays, the compounds were classified as established the Global Harmonized System of Classification and Labelling of Chemicals (GHS). According to the criteria of the European Medicines Agency (EMEA) the real risk of impact of these compounds in the environment was predicted. Following this methodology and for aquatic environments, clofibric acid, clofibrate and cefaclor can be classified as risk-free. By applying the criteria of the Phase II A of EMEA, three compounds (Ibuprofen, omeprazole and acetaminophen) have resulted with high environmental risk. Nevertheless, applying the Phase II B of EMEA, only the metabolite 1, 4-benzoquinone presents high environmental risk. The ERA on WWTPs indicates that ibuprofen, ciprofloxacin, naproxen and acetaminophen show some type of risk (Tier A). Ibuprofen and ciprofloxacin highlight in Tier B with a low risk. In any case, it is necessary to improve acute and chronic ecotoxicity tests and the estimation of predicted environmental concentrations (PECs) of PPCPs to support these studies.