Liquid chromatography coupled to atmospheric-pressure ionization mass spectrometry (LC-API-MS) with negative ion detection was studied for the determination of a variety of phenolic compounds in environmental waters. An isocratic mobile phase of 0.05% acetic acid-acetonitrile (50:50, v/v) was used. The influence of post-column addition of different bases on the sensitivity of the detection in electrospray (ES) was studied. The [M-H]-ion was the base peak for all the compounds using both ES and atmospheric-pressure chemical-ionization (APCI) ion sources. Moreover, abundant structural information was obtained by increasing the extraction voltage. Detection limits for standard solutions ranging from 2 to 13 ng injected for LC-ES-MS and from 0.02 to 20 ng for LC-APCI-MS were obtained. Good reproducibilities (day-to-day and run-to-run) were observed. The optimum LC-ES-MS and LC-APCI-MS conditions thus determined were used for a quantitative analysis of some phenolic compounds in spiked tap water and sea water samples.