Cryptand-like porphyrinoid assembled with three 2,6-dipyrrlpyridine chains binds alcohol at each molecular crevice in the C-3h symmetric conformation through three hydrogen bondings. This receptor binds dichloroacetic add at each crevice in the D-3 symmetric conformation, where strong positive allosteric effect was observed on the basis of the Hill plot with a Hill coefficient (n = 2.7 +/- 0.2), and the association constant (log K = 13.6 +/- 1.8). Ligand binding at the first crevice enhances polarization of the pi-conjugated chain to make pyrrole more acidic at the second crevice and pyridine more basic at the third crevice.