Hybrid multilayers of phthalocyanines (Pc) and titanium oxide (TiOx) have been effectively fabricated on the surfaces of quartz and indium-tin-oxide (ITO) according to the following layer-by-layer sequence; (i) the formation of a titanium butoxide layer (Ti(OBu)m) grafted onto the substrate surface by immersion of a substrate into a solution of Ti(OBu)4, (ii) hydrolysis of Ti(OBu)mto a TiOx layer with a Ti–OH surface, (iii) dipping of the treated substrate into a solution of Pc1–Pc3bearing four or eight (triethoxysilyl)alkoxy substituents to form a Pclayer on the TiOx surface, presumably through Ti–O–Si bonding, (iv) hydrolysis of excess Si(OEt)3groups in the Pclayer to form a silanol surface and (v) cyclic repetition of steps (i)–(iv). Atomic force microscopy (AFM) has shown that the multilayer surfaces are smooth, with surface roughnesses similar to that of a pristine substrate. The ratios of Ti atoms/Pcmolecule for three different multilayers determined by X-ray photoelectron spectroscopy (XPS) were found to be roughly constant (3.8–4.3). For hole-only diodes of ITO/N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine/Au, it has been found that the surface modification of ITO with the hybrid multilayers of Pc1causes remarkable current enhancements at low applied biases depending on the cycle number of the layer-by-layer deposition. [ABSTRACT FROM AUTHOR]