Stable synthetic bilayer membranes with Cu2+-coordinated headgroups can be formed by the series of single-chain amphiphiles, CnH2n+1NHC2H4NH2 (n = 8, 12, 14, 16, 18), in dilute aqueous Cu(NO3)(2). The novel structural features of the membrane system have been investigated thoroughly via X-ray diffraction (XRD), Fourier transform Raman (FT-Raman) and infrared(FT-IR), and electronic reflectance spectroscopies. Two bilayer packing fashions were conclusively proposed : the tail-to-tail model for the n = 8 amphiphiles and the interdigitation one for the n > 8 amphiphiles. It was revealed at the molecular level that the balance and matching between the headgroup coordination and the hydrophobic assembly of the alkyl chains endow the complexed bilayer membranes with structural varieties.