The present endeavor focuses on the unusual interactions between polyaniline and graphene oxide (PANi–GO) which radically affects the properties of nanocomposites as it is an emerging material for many potential applications. A series of nanocomposites have been synthesized by varying the weight percentage of highly nonconducting GO with respect to aniline which exhibit superior properties in terms of shelf life, processability and conductivity due to the synergistic effect of GO and PANi. A comparison of the resistances of samples reveal that though as-synthesized GO is insulating (80 MΩ), when added to PANi (283 kΩ) in small amounts yields conducting composites (50–280 Ω). Up to 5 weight % concentration, GO renders conductivity to the composite probably by increasing the doping level of PANi. Nonetheless, no further increase in conductivity observed on addition of more than 5 wt% GO in the composite has dictated us to unravel the structure property relationship between PANi and GO, where GO facilitates the formation of partially reduced phase of PANi, thereby restricting the electronic transport. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3778–3786. © 2016 Wiley Periodicals, Inc.