A series of meso-(4-(N,N-dibenzylamino)phenyl)-substituted subporphyrins was synthesized by means of Buchwald-Hartwig amination protocol. Substitution of the amino group at the 4-position of the meso-phenyl substituent resulted in a remarkable red shift in the absorption spectra and drastic enhancement of fluorescence intensity probably as a consequence of intramolecular CT interaction. These characteristics have been utilized to construct a cation-sensing system by appending a 1-aza-15-crown-5 unit to subporphyrin that displays large spectral changes upon cation binding.