The simultaneous spectrofluorimetric determination of aromatic polycyclic hydrocarbons of environmental interest, namely benzo[a]pyrene. benzo[e]pyrene, benzo[ghi]perylene, coronene, dibenzo[a,h]anthracene and indeno[1,2,3-cd]pyrene, in micellar media by using the non-ionic surfactant polyoxyethylene 10 lauryl ether (POLE) was investigated. In order to employ the highest sensitivity signals for the determination of each of the compounds in the mixture, the corresponding linear variable angle fluorescence spectra were recorded. Owing to the high spectral overlap observed, resolution of the multicomponent system was carried out by applying known algorithms such as multiple linear regression, partial least squares regression type 1 and artificial neural networks. The results obtained for both synthetic mixtures and water samples of two different origins spiked with known amounts of hydrocarbons of interest were satisfactory.