The goal of this work is to investigate the morphology, electrical and optical properties of undoped ZnO (i-ZnO) thin layers deposited on Si substrates with (100) and (111) orientations. Plasma enhanced metalorganic chemical vapor deposition (PEMOCVD) was used for the deposition of i-ZnO layers at different temperatures. Atomic force microscopy (AFM), ellipsometry and four-probe method were used for the analysis. It is found that substrate orientation and growth temperature determine the morphological (grains size, surface roughness) as well as electrical properties of ZnO films. It is shown that the refractive index value depends on the surface morphology. It is concluded that properties of i-ZnO layers deposited on different Si substrates at different conditions exhibit some trends and peculiarities, which have to be taken into account for the processing of heterojunction solar cells by the PEMOCVD method. © 2007 Elsevier B.V. All rights reserved.