A series of complexes of the type [Ti(′Cp)₂Y] {′Cp = η⁵-C₅H₅ (Cp), η⁵-C₅H₄SiMe₃ (^SiCp), η⁵-1,3-C₅H₃(Me₃Si)₂ (^Si2Cp); Y = Cl⁻, CN⁻, NCS⁻, NCSe⁻, dicyanamide (dca), tricyanomethanide (tcm) and 1,2,3,4-thiatriazol-5-thiolate (ttt)} were prepared and studied by ESR spectroscopy. Ring-substituted compounds [Ti(^SiCp)₂Cl], [Ti(^Si2Cp)₂Cl], [Ti(^SiCp)₂CN] and [Ti(^Si2Cp)₂CN] dissolved in coordinating solvents exist in an equilibrium with solvated species. The thiatriazolthiolate ligand in complexes [Ti(′Cp)₂(ttt)] behaves as a S,N-chelator to yield a thermally unstable 4-membered chelate ring having the ESR signal with significant splitting due to coupling with one ¹⁴N nucleus. Solutions of [Ti(′Cp)₂Y] (Y = NCS⁻, NCSe⁻, dca and tcm) readily dissolve the additional pseudohalide salt giving anionic species [Ti(′Cp)₂Y₂]⁻ with a characteristic ESR pattern caused by super-hyperfine splitting by two ¹⁴N nuclei. Cyanide complexes dissolve additional KCN as well, but no coupling to ligand nuclei (neither ¹⁴N nor ¹³C) was observed. The frozen-solution ESR spectra of [Ti(^Si2Cp)₂Cl], [Ti(^Si2Cp)₂CN] and [Ti(′Cp)₂Y] (Y = NCS⁻, NCSe⁻ and ttt) are typical for monomeric species of rhombic symmetry. The remaining complexes form dimeric {[Ti(Cp)₂Cl]₂, [Ti(^SiCp)₂Cl]₂, [Ti(′Cp)₂dca]₂, and [Ti(′Cp)₂tcm]₂} or trimeric {[Ti(^SiCp)₂CN]₃} adducts under these conditions. The nuclearity of [Ti(Cp)₂CN] cannot be accurately determined by ESR spectroscopy due to its poor solubility but the presence of species with a higher spin ground state was confirmed (similar to the case of the above-mentioned dimers and trimer) by the observation of formally forbidden half-field transition. The reported results of the crystal structure analysis of [Ti(^SiCp)₂Cl], [Ti(Cp)₂tcm], [Ti(^SiCp)₂tcm], [Ti(^SiCp)₂dca], [Ti(^SiCp)₂CN], and [TiCp₂(NCS)]₂O corroborate the findings based on spectroscopic measurements.