This study aims to elucidate the effect of magnetic graphene oxide (GO) alignment in a polymer matrix on the ionic conduction and methanol barrier properties of the resulting composites. Magnetic iron oxide (Fe3O4) nanoparticles were fabricated and anchored on GO nanosheets. The magnetic GO-Fe3O4 nanofillers were incorporated into a quaternized polyvinyl alcohol (QPVA) matrix to form a polymeric composite. By applying a magnetic field (MF) along the in-plane direction during the drying and film formation steps, the GO-Fe3O4 nanosheets were aligned in an orientation parallel to the direction of the MF and connected to each other in elongated domains, as confirmed using transmission electron microscopy, field emission scanning electron microscopy/ energy dispersive X-ray spectroscopy mapping, and laser scanning microscopy. The MF-aligned QPVA/GO-Fe3O4 electrolyte possessed higher conductivity and lower permeability than the un-aligned QPVA/GO-Fe3O4 membrane and pristine QPVA film. The aligned QPVA/GO-Fe3O4 composite exhibited a peak power density of 172.4 mW cm(-2) at 60 degrees C, which is higher than those of the composite without the MF treatment (67.7 mW cm(-2)) and the pristine QPVA (50.3 mW cm(-2)). This research demonstrates the extraordinary benefits of MF assisted GO-Fe3O4 nanofillers in facilitating the ion conduction and barrier property of a polymeric composite at 0.1% filler loading.