Graphene oxide (GO) was solution mixed with poly (vinylidene fluoride) (PVDF) with an aim to enhance the ß-crystalline phase of PVDF, wherein GO concentration was varied from 0.05-0.5 wt%. The composite film obtained after solution mixing was dried and compression-molded at 240 °C, 20 MPa for 5 min. Morphological observation via optical microscopic analysis indicated an increase in the remaining ‘agglomerate’ size and ‘agglomerate’ size distribution of GO in the PVDF matrix with an increase in filler concentration. Further, FEG-SEM observation suggested the dispersion of layered GO in the corresponding nano-composite. FTIR spectroscopy and WAXD analysis showed an increase in the ß-crystalline phase of PVDF as a function of GO concentration. In this context, the extent of interfacial interaction between PVDF and GO has been evaluated and correlated to the extent of ß-phase formation and their piezoelectric behavior. Moreover, DSC and SAXS studies were also carried out to understand the variation of the crystalline structure of PVDF due to the incorporation of GO. Further, PVDF/GO nanocomposites were also prepared and evaluated, wherein GO was ultra-sonicated followed by centrifuged prior to high-shear mixing with PVDF. An attempt has been made to relate GO dispersion-interfacial interaction-crystalline structure-piezoelectric properties of GO-based PVDF nano-composites.