For the purpose of revealing the spectra characteristics of methyl and ethanol, and establishing a method for distinguishing each other, the fluorescence features of methyl and ethanol were studied by three-dimensional fluorescence excitation-emission matrix spectra. The results obtained showed that there were two peaks in the three-dimensional fluorescence excitation-emission matrix spectra of methyl, and the intensities of the two peaks were positively related to the concentration of methyl when it was less than 15%. On the other hand, a whole fluorescence peak was only observed in the three-dimensional fluorescence excitation-emission matrix spectra of ethanol, and the intensity of the peak was positively correlated to the content of ethanol when it was less than 50%. There was a higher fluorescence efficiency for the methanol as compared to the ethanol. When the methyl was used for organic solvents to study the fluorescent nature of the organic matter, the fluorescence emitted by the methyl should be deduced. The locations of the fluorescence peaks of the methyl and ethanol were different. The peaks of the methyl were located at 225/350 nm and 250/375 nm, while the peak of the ethanol was characterized by 240/310 nm. Therefore, the fluorescence peak locations of the two alcohols could be applied to discriminate each other.