In order to enhance the dispersion and the interface in epoxy nanocomposites filled nanoparticles, a novel side‐chain liquid crystalline epoxy polymer (SLCEP) was synthesized. The SLCEP grafted to alumina (Al2O3) surfaces via the carboxyl group for dispersing nanoparticles, bonded covalently with the epoxy matrix by the epoxy group for interface improvement and maintained good liquid crystal properties by the mesogenic unit. The dispersity of Al2O3 in Al2O3‐SLCEP and epoxy nanocomposites were studied by Fourier transform infrared imaging system and field emission scanning electron microscopy. The interface of epoxy nanocomposites was researched by observing the fracture morphology. By preventing the agglomeration of Al2O3 and strengthening its interfacial bonding with the matrix, the glass transition temperature and thermal stability of Al2O3‐SLCEP/epoxy nanocomposites were improved distinctly, and Al2O3‐SLCEP/epoxy nanocomposites were much superior to neat epoxy in mechanical properties. The excellent performance of SLCEP modified nanoparticles in epoxy demonstrates that is an effective general approach for nanoparticle/polymer.

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