The emulsification of oil in water by nanoparticles can be facilitated by the addition of costabilizers, such as polymers and surfactants. The enhanced properties of the resulting emulsions are usually attributed to nanoparticle/costabilizer synergy; however, the mechanism of this synergistic effect and its impacts on emulsion stability and microstructure remain unclear. Here, we study the synergistic interaction of graphene oxide (GO) and a high molecular weight anionic polyacrylamide (PAM) in stabilization of paraffin oil/water emulsion systems. We show that the addition of PAM reduces the amount of GO required to stabilize an emulsion significantly. In order to probe the synergistic effect of GO and PAM, we analytically analyze the oil-free GO and GO-PAM dispersions and directly image their morphology via Cryo-TEM and atomic force microscopy (AFM). X-ray diffraction results confirm the adsorption of PAM molecules onto GO sheets resulting in the formation of ultimate GO-PAM complexes. The adsorption phenomenon is a consequence of hydrogen bonding and acid-base interactions, conceivably leading to a resilient electron-donor-acceptor complex. The microstructure of emulsions is captured with two-color fluorescent microscopy and Cryo-TEM. The acquired images display the localization of GO-PAM complexes at the interface while large amount of GO-PAM flocs coexist at the interface and in between oil droplets. Localization of such complexes and flocs at the interface is found to be responsible for their slow creaming rates compared to their GO counterparts. Mechanical properties of both dispersions and emulsions are studied by shear rheology. Rheological measurements confirm that GO-PAM complexes have a higher desorption energy from the interface resulting in higher critical shear strain of GO-PAM emulsions. The results, with insights into both structure and rheology, form a foundational understanding for integration of other polymers and nanoparticles in emulsion systems, which enables efficient design of these systems for an application of interest.