Thermal interface materials (TIMs) are of ever-rising importance with the development of modern microelectronic devices. However, traditional TIMs exhibit low thermal conductivity even at high loading fractions. The use of high-aspect-ratio material is beneficial to achieve low percolation threshold for nanocomposites. In this work, single crystalline copper nanowires with large aspect ratio were used as filling materials for the first time. A thermal conductivity of 2.46 W/mK was obtained at an ultralow loading fraction, ∼0.9 vol %, which was enhanced by 1350% compared with plain matrix. Such an excellent performance makes copper nanowires attractive fillers for high-performance TIMs.