The structure factor S(Q), intensities and pair distribution function g(r) of liquid Ni-Cr-W superalloy at different temperatures have been measured by a hightemperature X-ray diffractometer. Coordination N min , correlation radius r c , the nearest atomic distance r 1 , solidification microstructure and compression performance have been studied. The results show that a pre-peak exists on the structure factor curve at the liquidus temperature, and a fine structure of equiaxed, globular and non-dendritic primary grains can be achieved by casting the alloy at liquidus temperature. Liquid structure feature of Ni-Cr-W superalloy is found to depend on temperature. During the solidification, some structural information carried by the medium-range order (MRO) structure is inherited from the melt to the microstructure, which is beneficial for grain refinement. The maximum yield strength measured from typical microstructure of the equiaxed and non-dendritic grains at 1400°C is 543 MPa. The results show that refinement and non-dendritic grain is beneficial to the improvement of the yield strength.