Multilayer assemblies were prepared by alternating acid and amine amphipliles of aliphatic and diacetylenic compounds in an effort to prepare polar molecular assemblies. Divalent cationic stabilization was required for floating diacetylenic acid monolayers. As a consequence of the deposition technique ionization in both acid and amine compounds was thus considered, and the isoelectric deposition process developed. Spectroscopic analysis showed at the isoelectric pH the alternated acid and amine monolayers to be deposited as fully ionized salts. Structural investigations showed the aliphatic assemblies to possess near vertical alignment of the deposited amphiphiles, whereas the diacetylenic compounds were tilted to accommodate the diyne functionality.