Synthesis of free-standing flexible Co-ZnO/PVDF composite films is realized by sol-gel technique. Modulation of the optical and microstructural properties of the above composite films with Co-doped nanocrystalline ZnO loading in PVDF matrix was studied critically. Uniform dispersion of Co-doped ZnO in PVDF matrix was indicated by SIMS studies. Information on the bonding environment was obtained from X-ray photoelectron spectroscopy and Raman spectroscopy studies. A very strong peak at similar to 695 eV for core level spectra of F1s along with those for C1s, Zn2p and Co2p dominated the XPS spectra of the composite films. Presence of the predominant beta-phase of PVDF along with peaks related to ZnO nanocrystals in the poled sample was observed in the Raman spectra.