The protonation abilities of phthalocyaninatometals (MPcs) increase but their stabilities reduce by the introduction of alkoxyl substituents at alpha position. In the toluene, the order of mono-protonation rate for the tetra-alpha-(2, 2, 4-trimethyl-3-pentoxy)phthalocyaninatometals sorts with the center metals is Zn>Co>Cu>Ni>Fe, which is opposite to the order of their wavelength difference between the Q bands and X bands. However, their mono-protonated species can be decomposed easily at the rate order FePc>CoPc>CuPc>NiPc>ZnPc, analogous to their decomposition abilities in the benzoylperoxide (BPO) oxidation. In addition, it is interesting that a more remarkable decomposition is found when partial CuPc was mono-protonated.