Alloy interface materials with excellent thermal contact resistance elimination rate are widely used in the electronics industry to improve the thermal conductivity between material contact surfaces. In this paper, a novel Bi-In-Sn-Sb quaternary alloy was fabricated by adding a small amount of expandable metal Sb to Bi-In-Sn ternary alloy and smelting it in a tube furnace at 700 ℃. This alloy has a low melting point (~ 61 ℃), high thermal conductivity (~ 23.8 W m-1 k-1) and extremely low thermal contact resistance (~ 12.3 mm2 K W-1). The eliminating efficiency of thermal resistance between ceramic substrates is up to 95.9%, which can greatly improve the heat transfer performance between the substrates. The results show that the volumetric expansion rate of Bi-In-Sn-Sb quaternary alloy is as high as 88.6% after phase change (at 80 ℃), which can effectively reduce the residue of air gap between interfaces and improve the quality of contact surfaces. Therefore, the expandable phase change Bi-In-Sn-Sb quaternary alloy most likely becomes a good candidate of high performance thermal interface materials.