In this work classification of several petroleum products (gasoline, diesel, and kerosene) and some organic solvents (hexane, paint thinner) using the excitation emission matrices fluorescence spectroscopy and multiway principal component analysis was achieved successfully. Twelve samples of each of the above substances were studied; the total number of the neat samples including the petroleum and organic samples was 60 samples. The same protocol used above for classification was also used successfully for uncovering the adulterated gasoline with less expensive petroleum or organic substances of different compositions, namely, 2, 5, 10, and 20% v/v. Similar composition ratios were also used to uncover the adulteration of diesel with kerosene. Semiquantitative information in case of adulterating the gasoline with diesel was also possible.