The simple approach to acquire the fltaxescenee spectra of vitamin bl, b2 and t6 is proposed by direct ilhanination on solid powder sample. The experimentally acquired fluorescence spectra are in accordance with the previous measurements on soluble samples. The fluorescence spectra for a mixture of vitamins bl, b2 and b6 with different concentrations have been investigated, and the fluorescence mechanism is explained on the basis of moleoalar struchture Possible reasons of the blue-shift of the fluorescence peak and enhancement of the peak power are explained as well. The advantages of solid powder method is analyzed and discussed.