To probe the effects that self-assembled multilayers may have on electronic properties of a conductive surface, we carried out layer-by-layer depositions of organic/polymeric thin films on indium tin oxide (ITO) substrates. The organic/polymeric thin films were prepared by alternatively dipping ITO substrates in an oligomeric viologen or oligo(hexylene 4,4 ' -bipyridinum dibromide) solution and a macrocyle NiPc or nickel phthalocyanine solution. A linear relationship, between the optical absorption at 634 nm from NiPc and 274 nm from oligomeric viologen and the number of depositions, was observed in the UV-vis spectra. The multilayer structures were characterized with X-ray reflectometry, which yielded an average mean thickness of 1.5-2.0 nm per layer-pair. Taking advantage of the conductive surfaces, we performed surface infrared (IR) spectroscopy on oligomeric viologen and NiPc multilayers at an external grazing-angle reflection configuration. IR spectra with polarization perpendicular to the conductive ITO surfaces revealed a vibration band at 1227 cm(-1) corresponding to formation of the salt bridge binding Of -SO3-. . . Py+-R between viologen and NiPc. The results from Kelvin probe measurements showed an oscillating behavior of the surface electronic potential, as the surface layer was alternated between oligomeric viologen and NiPc. The average gap of this surface potential difference between viologen and NiPc layers is about 400 mV. We attribute the changes in surface potential or work function induced by oligomeric viologen or NiPc to the modulation in electron affinity rather than band bending at ITO surfaces, which is consistent with the surface photovoltage measurements. In addition, we find that the change in photoinduced band bending is a very weak periodic function of the number of self-assembled layers (viologen or NiPc).