Low-temperature vibronic spectra of two fulleropyrrolidines (1-methyl-3,4-FP and 1-methyl-2(4-pyridine)-3,4-FP) embedded in crystalline toluene matrix have been studied. Two-component composition of the spectra has been established and chargetransfer-excitation origin of the structureless component has been suggested. Fine-structured Shpol'skii spectra were observed for 1-methyl-3,4-FP, which made possible to perform the vibrational analysis of its vibronic spectra. General similarities of the absorption spectra of fulleropyrrolidines and C 60 molecules along with significant difference in their details have been discussed. A detailed interpretation of the C 60 spectra serves as a basis for analyzing the spectra of the derivatives. Quantum-chemical study is based on the effectivelyunpaired-electron concept for the fullerene molecule. Computations have been performed for the singlet states of the molecules in unrestricted Hartree-Fock approximation implemented in AM1 semiempirical quantum chemical codes of the CLUSTER-Z1 software. The population of the HOMO and LUMO of the molecules under study alongside with the lowering of the molecules symmetry have been proposed to explain the spectral features observed.