A series of dendritic multiporphyrin arrays (PZnTz-nPFB; n = 2, 4, 8) comprising a triazole-bearing focal zinc porphyrin (PZn) with a different number of freebase porphyrin (PFB) wings has been synthesized, and their photoinduced energy transfer process has been evaluated. UV/vis absorption, emission, and time-resolved fluorescence measurements indicated that efficient excitation energy transfer takes place from the focal PZn to PFB wings in PZnTz-nPFB's. The triazole-bearing PZn effectively formed host-guest complexes with anionic species by means of axial coordination with the aid of multiple C-H hydrogen bonds. By addition of various anionic guests to PZnTz and PZnTz-nPFB's, strong bathochromic shifts of PZn absorption were observed, indicating the HOMO-LUMO gap (ΔEHOMO-LUMO) of PZn decreased by anion binding. Time-resolved fluorescence measurements revealed that the fluorescence emission predominantly takes place from PZn in PZnTz-nPFB's after the addition of CN-. This change was reversible because a treatment with a silver strip to remove CN- fully recovered the original energy transfer process from the focal PZn to PFB wings.