A new spectral imaging approach, based on an imaging microscope coupled to a Fourier transform spectrometer, was applied for direct analysis of polycyclic aromatic hydrocarbons (PAHs) deposited onto solid matrices. Single crystals of several PAHs were grown and their fluorescence spectra were analyzed. The fluorescence characteristics, related to analytical reliable quantification of solid PAH compounds, were investigated. In particular, we have addressed the following parameters: (a) crystal-alignment effects upon the read-outs of the microscopic imaging set-up; (b) effects associated with either the crystal edge or the crystal surface originated fluorescence spectra; (c) inter-crystal self-absorption related processes. The understanding of these effects is important for a proper sampling of the PAHs and is essential for obtaining reliable quantification.