High-performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry (APCI-MS) in the negative-ion mode has been succesfully used for qualitative and quantitative determination of fifteen phenolic compounds found in olive mill wastewater. APCI gives information about both the molecular weight of these molecules and about their structure, showing consistent collision-induced dissociation pathways, which have been elucidated to give detailed information about the structure of the fragments. Quantitative analysis, using p-bromophenol as an internal standard, was carried out using calibration graphs for injections in the 0.01-1000 ng range, working both in scanning and selected-ion monitoring data aquisition modes, resulting in correlation coefficients higher than 0.98 for all compounds.