Low-cost thermal interface materials with high thermal conductivity (κ) and low total thermal resistance (Rt) receive considerable attention for thermal management. A copper film (CuFilm) is an excellent candidate due to the high κ (364 Wm−1 K−1) it possesses. However, the practical implementation is hindered by its high elastic modulus (Es = 70.8 GPa), inducing a high contact thermal resistance (Rc = 91.6 mm2 K W−1). Herein, the selective construction of electrically conducting or insulating layers on CuFilm to dramatically decrease Es, Rc, and Rt is reported. The highly electrically and thermally conducting layer is synthesized by incorporating in situ reduced copper nanoparticles (CuNPs, 35 vol%) and multiwalled carbon nanotubes embellished with CuNPs (1.5 vol%) in polyethylene glycol. The high effective κ (92.7 Wm−1 K−1) still maintains a low specimen thermal resistance (Rs = 4.9 mm2 K W−1), while the dramatically softened surface (Es = 5.7 GPa) decreases Rc (8.3 mm2 K W−1), resulting in a very small Rt (13.2 mm2 K W−1). Alternatively, the electrically insulating but thermally conducting layer is constructed using aluminum nitride particles. The κ is still high (72.1 Wm−1 K−1) with a small Rt (47.5 mm2 K W−1). The facile fabrication based on a CuFilm enables cost-effective thermal interface materials with tunable electrical and thermal properties.