Cu-Ni-P films with different morphologies were fabricated via electroless deposition route, due to the crystalline modification of polyethylene glycol (PEG). Effect of PEG molecular weight on morphology and structure of Cu-Ni-P films were investigated by field emission scanning electron microscopy and X-ray diffractometer. SEM observation reveals that electrolytes containing PEG 2000, 10000 and 20000, respectively can result in the formation of three kinds of unique architectures: pyramid with star-shaped cross section, cone and column. As PEG molecular weight increases, volume of the as-prepared microstructures increases but density decreases. The XRD pattern indicates the Cu-Ni-P coating is well-crystallized and preferred orientation formed in electrolyte without PEG, with PEG 2000, PEG 10000 and PEG 20000 are (1 1 1), (2 2 0), (1 1 1) and (1 1 1), respectively. Based on the proposition that properties of materials were affected by their size and morphology, wettability of the as-prepared Cu-Ni-P films were investigated. The hydrophobicity of coating deposited with PEG 2000 reached a climax exhibiting a contact angle of 123.8 degrees. Crown Copyright (C) 2012 Published by Elsevier B. V. All rights reserved.