How　to　adjust　the　microstructure,　macroproperties　and　function　of　prophyrins　by　tuning　the　substituents　and　central　metal　ions　species　has　been　the　key　and　the　challenge　problem　for　designing　the　high　activity　and　selectivity　catalysts.　It　can　provide　important　theoretical　foundation　for　the　accurate　designing　of　metalloporphyrin　catalysts　to　study　the　effects　of　the　substituents　and　central　metal　ions　on　the　electronic　structure　properties　of　porphyrins.　In　order　to　understand　the　relationship　between　microstructure　and　macro　catalytic　efficiency　of　porphyrins　in　essence,　the　electronic　structures　of　metalloporphyrins　with　different　substituents　(-OCH3,　-CH3,　-H,　-NO2)　and　different　central　metal　ions　(Mn,　Fe,　Co,　Cu,　Zn)　were　investigated　using　computational　chemistry　method　based　on　density　functional.　The　results　indicated　that　the　electron-withdrawing　substituent　(-NO2)　lowered　the　levels　of　the　highest　occupied　orbitals　(HOMO)　and　lowest　unoccupied　orbital　(LUMO)　of　metalloporphyrins.　Whereas　the　electron-donating　substitutes　increased　the　levels　of　the　HOMO　and　LUMO　of　metalloporphyrins.　The　central　metal　ions　have　an　effect　on　the　distribution　of　frontier　molecular　orbital.　The　frontier　molecular　orbitals　of　variant　valence　metalloporphyrins　(Mn,　Fe,　Co)　were　mainly　composed　of　3　d　orbital　of　metal　ions,　which　facilitated　the　activation　of　dioxygen.　The　frontier　molecular　orbitals　of　invariant　valence　metalloporphyrins　(Cu,　Zn)　were　composed　of　large　π　bond　from　porphyrin　ligands.　The　electrons　could　transport　fluently　in　the　large　π　bond,　therefore　the　invariant　valence　metalloporphyrins　also　have　the　high　activity.　Fukui　function　suggested　that　the　active　sites　of　variant　valence　metalloporphyrins　located　on　the　central　metal　ions.　Whereas　the　active　sites　of　invariant　valence　metalloporphyrins　might　locate　on　the　porphyrin　ligands.　©　All　Rights　Reserved.