In this review article, we describe metallophtahlocyanine (MPc)-catalyzed carbon-hydrogen bond activation in homogeneous media. Selective hydroxylation of hydrocarbons to the corresponding alcohols with molecular oxygen in the presence of MPc (M = Fe, Cr, and Fe in the +2 and +3 oxidation states) has been achieved under mild conditions. Azido complexes of MPc’s with metals at the +3 oxidation state are more reactive, suggesting the strong promotional effects of azido anion. Fluorination of Pc’S increases the reactivity and the stability of MPc’s. Product selectivity and catalyst stability are also improved by encapsulation of MPc’s in wide-bored zeolites. Further improvements in product selectivity and catalyst stability have been achieved by embedding the MPc-zeolites in the membranes of polydimethylsiloxanes. The large kinetic isotopic effects and the reactivity order of tertiary > secondary > primary C-H bonds reported for (Pc)Fe-catalyzed oxidations are consistent with oxidation by a high valent Fe=O complex as the rate-limiting step. For C-H bond activation under reducing conditions, [(R₈Pc)Rh]₂ (R = n-pentyl) has been found to activate the aromatic and all the C-H bonds of the pentyl group at high temperatures. The results are consistent with a free radical mechanism initiated by homolysis of the Rh-Rh bond to generate (R₈Pc)Rh radical. The hydride complex (R₈Pc)RhH, which is generated in the hydrogen atom abstraction by the (R₈Pc)Rh radical, dimerizes in non-polar solvents to form the hydride-bridged dimmer (R₈PcH)Rh(μ-H)Rh(R₈Pc)H (R₈PcH = R₈Pc with one of its meso nitrogens protonated). The characterization of this unusual complex and its equilibration with three of its isomers are described. Also described are rotational isomerisms of (R₈PcH)Rh(μ-H)Rh(R₈Pc)H and its non-bridged isomer, the Rh-Rh bonded dimer [(R₈Pc)Rh]₂, and the dimeric aggregates of (R₈Pc)Rh-Me.