In this study, we describe the formation of ZnO nanolayers inside the air capillaries of a silica photonic crystal fibre (PCF), targeting random laser and organic vapor sensing applications. ZnO nanolayers were developed by infiltrating the capillaries of the silica PCF with Zn-acetate/methanol solutions of various concentrations, followed by annealing treatments. The growth and morphology of the synthesized ZnO nanolayers were characterized by means of scanning electron microscopy (SEM) and found to be affected by the concentration of the Zn-acetate/methanol infiltration solution. For low concentrations, inspection with SEM revealed the formation of 25 and 100-nm-thick ZnO nanolayers across the entire length of the infiltrated capillaries, whereas increasing the Zn-acetate concentration resulted to the formation of randomly placed isolated ZnO nanorods. Room temperature photoluminescence spectra of the ZnO nanolayers inside the PCF were measured and compared with the corresponding spectra reported for ZnO structures formed on typical surfaces. (C) 2013 Elsevier B.V. All rights reserved.