The invention discloses high-Mo Ni3Al-based monocrystal high-temperature alloy modified by rare earth and a preparation method of the high-Mo Ni3Al-based monocrystal high-temperature alloy and belongs to the technical field of high-temperature alloy. The alloy comprises Ni, Al, Mo, Re, Ta, Cr, C, Y and Dy or Ce, an alloy casting-state structure comprises three phase structures including the gamma' phase, the gamma phase and the white precipitated phase rich in Mo and Re, the density is 7.9-8.1 g/cm<3>, and the alloy can reach the complete oxidization resistance level or the oxidization resistance level or the secondary oxidization resistance level at the temperature of 1100 DEG C. The method comprises the steps of preparing a liquid metal cooling medium, preparing a mother alloy bar, preparing Ni3Al-based monocrystal alloy seed crystals not containing rare earth elements, preparing high-Mo Ni3Al-based high-temperature alloy containing the rare earth elements through a direction monocrystal furnace, and conducting post heat treatment. The Ni3Al-based monocrystal high-temperature alloy provided by the invention is low in density and can meet the low-density requirement of aircraft engines, and the oxidization resistance of the alloy can reach the complete oxidization resistance level or the oxidization resistance level or the secondary oxidization resistance level at the temperature of 1100 DEG C.