It is demonstrated that a graphene-based film (GBF) functionalized with silane molecules strongly enhances thermal performance. The resistance temperature detector results show that the inclusion of silane molecules doubles the heat spreading ability. Furthermore, molecular dynamics simulations show that the thermal conductivity () of the GBF increased by 15%-56% with respect to the number density of molecules compared to that with the nonfunctionalized graphene substrate. This increase in is attributed to the enhanced in-plane heat conduction of the GBF, resulting from the simultaneous increase of the thermal resistance between the GBF and the functionalized substrate limiting cross-plane phonon scattering. Enhancement of the thermal performance by inserting silane-functionalized molecules is important for the development of next-generation electronic devices and proposed application of GBFs for thermal management.