Binuclear titanocene complexes [Cp 2Ti(tcm)] 2O ( 4), [Cp 2Ti(dca)] 2O ( 5) and [Cp 2Ti(dcnm)] 2O ( 6) (tcm − = tricyanomethanide, dca − = dicyanamide and dcnm − = dicyanonitrosomethanide) were synthesized in moderate yields by the reaction of Cp 2TiCl 2 ( 1) with respective alkali metal pseudohalide salts in the aqueous solution. When the reaction was carried out in dry organic solvents, mononuclear compounds Cp 2Ti(tcm) 2 ( 2) and Cp 2Ti(dca) 2 ( 3) were isolated. Preparation of dipseudohalide complex Cp 2Ti(dcnm) 2 by this manner was unsuccessful due to decomposition of dcnm ligand resulting in formation of oxygen-bridged compound 6. All prepared compounds were characterized by elemental analysis, NMR, Raman, infrared and UV–Vis spectroscopy. Molecular structures of 2, 4 and 6 (two polymorphs) have been determined by single-crystal X-ray diffraction analysis.