The synthesis of (porphyrinato)Sn-viologen, 1, and its supramolecular complexation with cucurbit[7]uril (CB[7]) were studied. 1H NMR spectroscopic studies obviously reveal that 1 forms a 1 : 2 supramolecular complex with CB[7] through the inclusion of viologen moieties of 1 into the cavity of CB[7]. The cyclic voltammetric study supports that the binding affinity of the radical cation forms is comparable to that of the di-cation viologen toward CB[7]. The fluorescence arising from the porphyrin moiety is significantly quenched upon the complexation of 1 with CB[7]. The ps-time-resolved fluorescence and ns-transient absorption spectroscopic studies reveal that the photoinduced electron transfer (PET) between viologen and Sn(iv) porphyrin of 1 takes place from the first excited singlet (S1) state and the second excited triplet (T2) state of the porphyrin moiety upon complexation with CB[7], while the PET from the S1 state is negligible in the absence of CB[7].