Capillary zone electrophoresis (CZE) with UV detection (254nm) was applied to characterize aquatic dissolved humic matter (DHM) from different environmental sources (lake, river and sea waters, in all 15 different samples). A series of separation examples of DHMs using a polyvinyl alcohol (PVA)-coated silica open tubular capillary were carried out in a phosphate buffer (40mM) as a background electrolyte at neutral acidity (pH 6.8). The separative power of electropherograms was reasonable and the reproducibility was above the mark. Each electropherogram was characteristic of the corresponding humic sample. Special functional fulvic and humic acids or their overall mixtures separated with XAD, DAX and DEAE sorbing solids as well as the original dissolved organic matter (DOM) were nicely differentiated according to their environmental sources. The PVA coating of open tubular silica capillaries seems to be very potential in electrophoretic characterization and separation of different humic solutes at neutral acidities with low sample concentrations thus permitting a workable technique, in a growing series of CZE studies, for better compared results from different studies.