The thiaporphyrin building blocks with N3S and N2S2 cores containing one hydroxyphenyl functional group at the meso position were synthesized by adopting the unsymmetrical thiophene diol method. These monohydroxy thiaporphyrins were used to construct the first examples of axial bonding type Sn(IV) porphyrin triads in which Sn(IV) porphyrin acts as basal unit and the two thiaporphyrin units as axial ligands by treating with SnTTP(OH)(2) in benzene at refluxing temperature, The axial bonding type triads were confirmed by mass, 1 D and 2D NMR studies. The absorption and electrochemical studies support weak ground state interaction among the porphyrin subunits within the porphyrin triads. The fluorescence studies indicate there is a possibility of energy transfer at the singlet state from basal Sn(IV) porphyrin unit to axial thiaporphyrin units.