This work describes a comparative study of tribo- and photoluminescence of metallocenes (Cp2HfCl2, Cp2TiCl2, Cp2ZrCl2, (CpMe)2ZrCl2, rac-Me2C(3-But-Cp)2ZrCl2, Ind*2ZrCl2). Occurring under mechanodestruction of polycrystals, triboluminescence of zirconium bis-cyclopentadienyl complexes, Cp2ZrCl2, (CpMe)2ZrCl2, and rac-Me2C(3-But-Cp)2ZrCl2 has been revealed for the first time. The triboluminescence spectrum in air is similar to the photoluminescence spectrum of zirconocene polycrystals. The triboluminescence spectrum does not show *N2 luminescence. Ne and Ar lines are observed in the triboluminescence spectrum in the atmosphere of these gases. An increase in the number of substituents in zirconocene ligands leads to a bathochromic shift of the emission band maximum in triboluminescence spectra of the complexes. Possible mechanisms of zirconocene triboluminescence excitation are discussed.