The easy method to construct c-axis oriented zinc oxide (ZnO) layer directly attached onto a transparent conducting substrate was studied. On the assumption that anionic organic functional groups serves as a directing group for Zn2+ ion, poly(sodium p-styrenesulfonate) (PSSNa) was immobilized onto ITO surface by layer-by-layer (LbL) process, and ZnO was electrodeposited onto the modified ITO surface. Nucleation of ZnO crystals was induced by LbL treatment and the nucleated crystals were aligned toward <0 0 1>. The ZnO crystals gradually formed a film as the electrolysis progressed maintaining the crystal alignment, resulted in (0 0 1)-oriented ZnO continuous film. The obtained ZnO film was more transparent and uniform, and exhibited more intense photoluminescence at UV region than those deposited on a bare ITO. Also, the present method for the orientation selective nucleation of ZnO crystals revealed to be utilized as a seed layer for well aligned ZnO nanopillar array. (C) 2013 Elsevier Ltd. All rights reserved.