The enhanced thermal diffusivity and mechanical properties of poly(l-lactic acid) (PLLA) nanocomposites reported here are based on the percolation network formed when PLLA is hybridized with short carbon fibers (CFs) and functionalized zinc oxide whiskers. The PLLA nanocomposite containing 30 wt% (a parts per thousand 9.5 vol%) ZnO whiskers and 10 wt% (a parts per thousand 8.1 vol%) CFs had a thermal diffusivity almost as high as that of stainless steel and an insulator-level electrical resistivity (> 10(10) Omega m). Modifying the surface of the ZnO whiskers by esterifying them using specific alcohols with long linear alkyl chains improved the elastic strength and toughness of the nanocomposites significantly. These results suggest that hybridizing PLLA with short CFs and functionalized ZnO whiskers yields nanocomposites with high thermal diffusivity as well as high electrical resistivity and excellent mechanical properties.