AbstractThis study is dedicated to the fabrication of acrylated epoxidized natural rubber (AENR)/dual‐functionalized organoclay (DF‐C30B) hybrid networks using an in‐situ light‐induced crosslinking polymerization technique. The process begins with the successful synthesis of DF‐C30B, which contains methacrylate groups, achieved by reacting 3‐methacryloxypropyltrimethoxysilane (MPS) with cloisite 30B (C30B). During fabrication, DF‐C30B nanolayers are dispersed within the AENR matrix at various feed ratios, ranging from 1 to 8 parts per hundred of rubber (phr). The photocrosslinking polymerization is then initiated using 2,2‐dimethoxy‐2‐phenylacetophenone (DMPA) as the photoinitiating agent. Subsequent analysis of the nanocomposites involves evaluating their structure and morphology using established techniques such as Fourier transform infrared (FTIR) spectroscopy, x‐ray diffraction (XRD), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The FTIR analysis enables comparing distinct bands of the nanocomposite's components, affirming the integration and covalent attachment of nanoclay in the AENR matrix. Results from TEM and XRD illustrate the uniform distribution of DF‐C30B throughout the AENR matrix without significant agglomeration. TGA results indicate that the hybrid networks exhibit enhanced thermal stability, with degradation onset temperatures of 306°C, 308°C, 315°C, and 318°C for DF‐C30B loadings of 1, 2, 4, and 8 phr, respectively, compared to 198°C for pure AENR. Correspondingly, char residue levels increased to 4.3%, 5.6%, 7.8%, and 11.7% for the respective DF‐C30B contents. This research underscores the promising role of DF‐C30B as a strengthening component in nanocomposites based on NR, contributing to improved thermal endurance, enhanced uniformity, and offering insightful directions for future advancements.Highlights Fabricated acrylated epoxidized natural rubber (AENR)/dual‐functionalized organoclay (DF‐C30B) hybrid networks via light‐induced crosslinking polymerization. Enhanced compatibility and performance of DF‐C30B within the AENR matrix. Successful integration and stability confirmed by Fourier transform infrared spectroscopy, x‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Uniform dispersion of DF‐C30B within the matrix demonstrated by XRD and TEM. Improved thermal stability compared to neat AENR, as evidenced by TGA results.