Thermal functional Materials have wide applications in thermal management fields, and inserting highly thermal conductive materials is effective in enhancing thermal conductivity of matrix. In this paper, copper nanoparticles were selected as the additive to prepare polymethyl methacrylate (PMMA) based nanocomposite with enhanced thermal properties. Uniform copper nanoparticles with pure face-centered lattice were prepared by liquid phase reduction method. Then, they were added into PMMA/N, N-Dimethylmethanamide (DMF) solution according to the different mass fraction for uniform dispersion. After DMF was evaporated, Cu-PMMA nanocomposites were gained. The thermal analysis measurement results showed that the decomposition temperature of nanocomposites decreased gradually with the increasing particle loadings. The thermal conductivity of the Cu-PMMA nanocomposites rose with the increasing contents of copper nanoparticles. With a 20 vol.% addition, the thermal conductivity was up to 1.2 W/m · K, a 380.5% increase compared to the pure PMMA. The results demonstrate that copper nanoparticles have great potential in enhancing thermal transport properties of polymer.