A detailed study of the reaction of the dinuclear [{Ti(η5-C5Me5)R2}2(μ-O)] (R = Me 1, CH2Ph 2) compounds with a series of organic isonitriles (R′NC, R′ = tBu, iPr, CH2SiMe3, Xyl) (Xyl = 2,6-Me2C6H3) and nitriles (R′CN, R′ = tBu, iPr, SiMe3) has been carried out. Single-crystal X-ray structural studies revealed a variety of reactivity and structural moieties. Theoretical calculations (density functional theory, DFT) were used to understand the mechanism of some uncommon reactions observed experimentally. Reactions of 1 and 2 with isocyanides tBuNC, iPrNC, and Me3SiCH2NC led to the formation of dimetallic η2-iminoacyl species [{Ti(η5-C5Me5)(R′NCR)R}2(μ-O)] (R = Me, R′ = tBu 3, iPr 4, CH2SiMe3 5; R = CH2Ph, R′ = CH2SiMe3 6). Complex 4 underwent net rearrangements at room temperature to give the imido-vinylamido derivative [Ti2(η5-C5Me5)2(μ-O)(μ-NiPr) {N(iPr)CMe═CMe2}Me] (7), whereas the reaction of complex 2 with XylNC rendered the N─C bond cleavage product [{Ti(η5-C5Me5)(CH═CHPh)}(μ-O)(μ-κ2-N,C─N(MeC6H3)CH2){Ti(η5-C5Me5)}] (8). The reactions of 1 with nitriles tBuCN and iPrCN gave the ketimido products [{Ti(η5-C5Me5)Me(CN(Me)R′)}2(μ-O)] (R′ = tBu 9, iPr 10), whereas the analogous processes with 2 gave the alkenyl-imido complexes [{Ti(η5-C5Me5)(CH2Ph)2}(μ-O){Ti(η5-C5Me5)(═NC(R′)═C(H)Ph)(NCR′)}] (R′ = tBu 11, iPr 12) with the concomitant coordination of a nitrile molecule. Complex 1 reacts with Me3SiCN to afford the nitrile–isonitrile isomerization product [{Ti(η5-C5Me5)Me2}(μ-O){Ti(η5-C5Me5)(κ2-C,N-Me2CNSiMe3)(CNSiMe3)] (13).