Fluorescence emission and excitation spectra of terrylene in several n-alkane Shpol’skii matrixes have been studied at liquid helium temperatures. The presence of two dominant Shpol’skii sites has been detected in all matrixes; we tentatively attribute one of the sites to terrylene substitutionally entering the host lattice, and the other one to guest molecules situated in the region of defects. The experiments, supported by quantum-chemical calculations, point to the existence of two stereoisomers of the solute. We found n-decane to form the best matrix for terrylene; the system seems to be suitable for single molecule spectroscopy studies.