Graphene presents an extremely ultra-high thermal conductivity, well above other known thermally conductive fillers. However, graphene tends to aggregate easily due to its strong intermolecular π–π interaction, resulting in poor dispersion in the polymer matrix. In this study, silver nanoparticles anchored reduced graphene oxide (Ag/rGO) were first prepared using one-pot synchronous reduction of Ag⁺ and GO solution via glucose. The thermally conductive (Ag/rGO)/polyimide ((Ag/rGO)/PI) nanocomposites were then obtained via electrospinning the in situ polymerized (Ag/rGO)/polyamide electrospun suspension followed by a hot-press technique. The thermal conductivity (λ), glass transition temperature (T_g), and heat resistance index (T_HRI) of the (Ag/rGO)/PI nanocomposites all increased with increasing the loading of Ag/rGO fillers. When the mass fraction of Ag/rGO (the weight ratio of rGO to Ag was 4:1) fillers was 15%, the corresponding (Ag/rGO)/PI nanocomposites showed a maximum λ of 2.12 W/(m K). The corresponding T_g and T_HRI values were also enhanced to 216.1 and 298.6 °C, respectively. Furthermore, thermal conductivities calculated by our established improved thermal conduction model were relatively closer to the experimental results than the results obtained from other classical models.