Mn-doped nanocrystalline ZnO was incorporated in polyvinylidene fluoride thin films for obtaining freestanding flexible films by sol-gel technique. The as-deposited and the poled composite Mn-ZnO/PVDF films contained three different amount of Mn doping in ZnO nanocrystals as Zn1-xMnxO (x = 0.01, 0.03 and 0.05). X-ray photoelectron spectroscopy (XPS) and X-ray near edge absorption (XANES) measurements have been carried out to investigate the valence states of the host and the dopant ions in the samples while local environments surrounding them have been studied critically using extended X-ray absorption fine structure (EXAFS) measurements. Information on the local structure surrounding the Zn and Mn sites was obtained to throw a clear insight on the bonding environment in the Mn-ZnO/PVDF films. (C) 2015 Elsevier Ltd. All rights reserved.