Fluorescence excitation and emission spectra of perylene in n-alkane Shpol'skii matrixes have been studied at liquid helium temperature. The presence of a dominant Shpol'skii site has been detected in all matrixes and attributed to perylene molecules substitutionally entering the host lattice. The character of the highest-energy site observed in all matrixes was found to be strongly dependent on the nature of solvent. Three matrixes were selected for a comparative study: n-hexane, forming a "good" matrix, and n-decane and n-undecane, forming "poor" matrixes. A vibrational analysis of all Shpol'skii sites was performed, and an additional low-frequency out-of-plane vibration at ca. 190 cm(-1) was observed for the highest energy site in n-decane and n-undecane matrixes in highly resolved two-dimensional spectra. Vibrational frequencies detected in "conventional" emission and excitation spectra and in two-dimensional spectra, as well as data from infrared and Raman spectra, are in a good agreement with recalculated vibrational frequencies obtained by MNDO and ab initio quantum-chemical methods.