M(por) (M =Rh and Co) (por =porphyrinato dianion) reacted selectively with isopropyl ketones at the carbon(CO)-carbon(α) bond under room temperature to give high yields of M Ⅲ(por) acyls and the corresponding oxidized carbonyl compounds up to 89 % yields.MⅢ(por)OH is proposed to be the C-C bond activation (CCA) intermediate.The stoichiometric reaction is further developed into the photocatalytic CCA both using UV and visible light sources (λ =405 nm).