This study reports on the evaluation of the CO donating behavior of tricarbonyl dichloro ruthenium(II) dimer ([Ru(CO)3Cl2]2) and 1,3-dimethoxyphenyl tricarbonyl chromium (C6H3(MeO)2Cr(CO)3) complex by UV-visible technique and electrochemical technique. The CO release was monitored by following the modifications of the UVvisible features of MbFe(II) in phosphate buffer solution and the redox features of reduced Hemin, HmFe(II), confined at the surface of a vitreous carbon electrode. In the latter case, the interaction between the hemin-modified electrode and the released CO was seen through the observation of an increase of the reduction current related to the FeIII/FeII redox process of the immobilized porphyrin. While the ruthenium-based complex, ([Ru(CO)3Cl2]2), depended on the presence of Fe(II) species to release CO, it was found that the chromium-based complex released spontaneously CO. This was facilitated by illuminating and/or simple stirring of the solution containing the complex.