The　protonation　abilities　of　phthalocyaninatometals　(MPcs)　increase　but　their　stabilities　reduce　by　the　introduction　of　alkoxyl　substituents　at　α　position.　In　the　toluene,　the　order　of　mono-protonation　rate　for　the　tetra-α-(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.　©　2008　Elsevier　B.V.　All　rights　reserved.