A wet layer-by-layer self-assembled ZnO/polyaniline (PAN) composite films have been deposited on glass substrate using organic solutions. Films have been studied by transmission electron microscopy, FTIR and photoluminescence spectroscopy. The layer consists of almost spherical particles having sizes approximately ranging from 20 to 25 nm. The opto-electrical properties of the films have also been investigated. A violet emission has been noticed in the PL spectra. This is due to defect levels at the grain boundary area. IR data supported the chemical interaction between the components in neighboring layers. A significant photo-conduction of the composite films has been observed at the excitation wavelength of 350 nm. (c) 2007 Elsevier B.V. All rights reserved.