In enhanced oil recovery (EOR), the stability of polymeric systems in harsh reservoir conditions is significant. A proof of concept research on the application of supramolecular self-assembly for EOR is presented in this paper. The motivation was to acquire new insights on the effectiveness of these extended polymolecular assemblies with improved salinity and hardness tolerance and viscoelastic properties for EOR. The formation of these self-assemblies relies on noncovalent interactions that hold them together. The performance of two self-assembly systems derived from a partially hydrolyzed polyacrylamide (SAP-HPAM) and xanthan gum (SAP-XG) for heavy oil recovery was established and compared to the performance of a commercial hydrophobically modified polyacrylamide (HMSPAM). The SAP-HPAM produced 20% higher incremental heavy oil recovery than the baseline HPAM; while the SAP-XG does not show suitable propagation within the porous media. These experimental results provide new helpful insights for the technical and cost-effective optimization of these self-assembly compositions for EOR applications.