Products of petroleum crude are multifluorophoric in nature due to the presence of a mixture of a variety polycyclic aromatic hydrocarbons (PAHs). The use of excitation - emission matrix fluorescence (EEMF) spectroscopy for the analysis of such multifluorophoric samples is gaining progressive acceptance. In this work, EEMF spectroscopic data is processed using chemometric multivariate methods to develop a reliable calibration model for the quantitative determination of kerosene fraction present in petrol. The application of the N-way partial least squares regression (N-PLS) method was found to be very efficient for the estimation of kerosene fraction. A very good degree of accuracy of prediction, expressed in terms of root mean square error of prediction (RMSEP), was achieved at a kerosene fraction of 2.05%. ©2008 Society for Applied Spectroscopy.