Abstract <p>This study seeks to elucidate the effects of graphene oxide reduction and its functionalization with diazonium salts on the thermoelectric properties of ternary composites composed of polymer, graphene, and metal oxide, synthesized through micro-emulsion polymerization utilizing sodium dodecyl sulfate (SDS) as a surfactant. Specifically, two diazonium salts—4-(4-amino-2-hydroxyphenyl) diazenyl-benzene-sulfonate and 4-(4-aminophenyl) diazenyl-benzene-sulfonate—were synthesized to functionalize reduced graphene oxide. Subsequently, the ternary composites, designated as PPy/rGO/WO₃ and PPy/FrGO/WO₃, were developed employing four distinct synthesis protocols to assess the impact of the synthesis methodology on the thermoelectric characteristics of the resultant materials. This investigation also delves into the critical role of the sequence of constituent incorporation—namely polymer, graphene, and tungsten oxide—in influencing the morphology, physicochemical properties, and thermoelectric performance of the composites. This rigorous methodological framework enables the identification of the most effective synthesis protocol for optimizing thermoelectric performance. Comprehensive analyses conducted through techniques including Raman spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermoelectric measurements revealed a significant enhancement in the figure of merit (ZT), increasing from 150 to 250 when compared to polypyrrole alone. This finding underscores the transformative potential of the employed treatments and the resultant composites.</p> Graphical Abstract <p></p>