Synchronous spectrofluorimetry was carried out for the simultaneous determination of various polycyclic aromatic hydrocarbons(PAHs) in aqueous solution by fluorescence spectrometry have been studied. The optimal wavelength interval(Δλ) for synchronous spectra of acenaphthene, anthracene, benzo[a]anthracene, fluorene and pyrene were investigated in the presence of surfactants. The great enhancement of the fluorescence of these PAHs in Triton X-100 was obtained and optimal wavelength was 50 nm. The calibration curves in synthetic mixture solution of 5 PAHs were linear over the range from 1.0×10-8M to 1.0×10-4M. Under the optimal experimental conditions, the detection limits were 4.9×10-9M, 7.0×10-9M, 4.7×10-9M, 1.6×10-9M and 3.2×10-9M for acenaphthene, anthracene, benzo[a]anthracene, fluorene and pyrene, respectively.