Chemical bond is one of the most important yet fundamental concept in chemistry.Among these bonds three-electron σ-bond was a nonclassical one which was proposed by Linus Pauling in 1931[1].In the 20th century several compounds containing three-electron σ-bond were synthesized and recently Wang and colleagues reported three-electron σ-bond between chalcogens[2].However the investigation to the combination of three-electron σ-bond was still missing.Considering the rigidity as well as the ease of decoration of porphyrin ring,here we introduce porphyrin as a critical skeleton to support the Se…Se…Se moiety.Initially neutral multiphenylseleno porphyrins 1 and 2 were synthesized in good yields[3].Subsequently oxidation of compound 1 and 2 by using AgSbF6 or NOSbF6 led to the compound 3 and 4,respectively.Both the structures of 2 and 4 were characterized by 1H NMR,13C NMR and X-ray single crystal diffraction.