At the interface of the toluene/water system, H4TPyP4+ and CuTPPS4-formed heteroaggregates, which could recognize the chirality of D- and L-phenylalanines (Phe) and other amino acids, though neither H4TPyP4+ nor CuTPPS4- could indicate the chirality of the amino acids. The composition of H4TPyP4+:CuTPPS4- in the aggregate was estimated as 1:1 as reported in an aqueous solution. But, CD spectra of the interfacial heteroaggregates were different from that in the aqueous solution, suggesting different chiral interaction. The present results suggest a new mode of the interfacial chiral reaction exhibited by the synergistic effect of the heteroaggregation of the inversely charged porphyrins.