ABSTRACTIn this study, we report an effective method to fabricate high‐performance polyimide (PI)‐based nanocomposites using 3‐aminopropyltriethoxysilane functionalized graphene oxide (APTSi‐GO) as the reinforcing filler. APTSi‐GO nanosheets exhibit good dispersibility and compatibility with the polymer matrix because of the strong interfacial covalent interactions. PI‐based nanocomposites with different loadings of functionalized graphene nanosheets (FGNS) were prepared by in situ polymerization and thermal imidization. The mechanical performance, thermal stability, and electrical conductivity of the FGNS/PI nanocomposites are significantly improved compared with those of pure PI by adding only a small amount of FGNS. For example, a 79% improvement in the tensile strength and a 132% increase in the tensile modulus are achieved by adding 1.5 wt % FGNS. The electrical and thermal conductivities of 1.5 wt % FGNS/PI are 2.6 × 10−3 S/m and 0.321 W/m·K, respectively, which are ∼1010 and two times higher than those of pure PI. Furthermore, the incorporation of graphene significantly improves the glass‐transition temperature and thermal stability. The success of this approach provides a good rationale for developing multifunctional and high‐performance PI‐based composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42724.