We present the results of a reactivity study of titanium cationic clusters towards CO, C(2)H(2), C(2)H(4) and C(3)H(6) based on guided-ion-beam mass spectrometry and DFT calculations. We identified Ti(2)O(4)(+) and to a lesser extent TiO(2)(+) species which preferentially undergo oxidation reactions. An oxygen centered radical of Ti(2)O(4)(+) is responsible for selective oxidation. Energy profiles and MD simulations reveal the mechanisms of the reactions. Regeneration of the oxygen centered radical was achieved experimentally and theoretically through the reaction of N(2)O with Ti(2)O(3)(+).