AbstractWith the rapid development of modern transportation systems, optimizing the relationship between structure and performance to obtain natural rubber‐based nanocomposites with excellent comprehensive performance is still worth to investigation. Herein, the regulation of flocculation potential through different flocculants selection on the thermomechanical properties for carbon black/graphene oxide reinforced natural rubber (CB/GO/NR) nanocomposites were investigated based on the compression electric double layer theory. The results showed that formic acid owned the highest zeta potential with comparison of sodium chloride (NaCl), calcium chloride (CaCl2), and aluminum chloride (AlCl3). Meanwhile, as the content was 8 wt%, tensile strength, tearing strength and thermal conductivity could achieve to 27.64 MPa, 56.89 N/mm, and 1.05 W m−1 K−1, respectively. While the heat generation after compression fatigue dropped to 10.1°C. These findings reveal that the highest zeta potential of formic acid could promote the improvement of flocculation degree between GO and NR latex and significantly enhanced the thermomechanical properties of CB/GO/NR nanocomposites due to the larger flocculation potential difference. Therefore, this study not only provides important theoretical insights for preparing high‐performance NR‐based nanocomposites, but also highlights the crucial role of high zeta potential flocculants in optimizing the composite performance. More importantly, the findings offer the creative insights for preparation of the excellent comprehensive NR nanocomposites for the practical industry application.Highlights The effect of flocculation degree on the properties of CB/GO/NR composites was studied. Formic acid was benefit to the flocculation and could promote the surface interaction. CB/GO/NR composites possessed the improved thermal and mechanical properties.