The quasi-line fluorescence and excitation spectra of 2-naphthylphenylcarbene (2-NPC) in n-hexane and 12-heptane Shpolskii matrices at 4.2 K are composed of several spectra with origins shifted by 30-300 cm(-1) from each other. They have been attributed to the triplet-triplet transition of the syn and anti conformers of 2-NPC, each one being trapped in several different sites of the matrix. This attribution has been confirmed by the EPR experiments performed at 77 K. Furthermore, the fluorescence and EPR spectra reveal the light-induced transformation of the syn 2-NPC into the anti 2-NPC conformer in the n-heptane matrix. The fluorescence decays of 2-NPC in both matrices at 4.2 K are nonexponential and attributed to the emission from different sublevels of the first excited triplet state T-1. The zero-field splitting parameter D(T-1) = 0.011 cm(-1) in the T-1 state of 2-NPC has been estimated from the magnetic field effect on the fluorescence decays. cm This value is much smaller than the D(T-0) = 0.41 cm(-1) value in the ground state T-0 of 2-NPC determined by EPR, which indicates the delocalization of the pi electron density onto the aromatic rings upon excitation.