Cu 71Al 25Ni 4 (mole fraction,%) shape memory alloy ribbons exhibit a good shape memory effect, which were prepared by melt-spinning technique. The microstructure of the as-spun ribbons was identified by D/Max-rA X-ray diffractometer. The order degree of martensite increases with decreasing liquid quenching temperature at the same quenching rate. The liquid structure of Cu 75Al 25 and Cu 71Al 25Ni 4 was investigated using X-ray diffraction method. The distinct pre-peaks have been found in front of main peaks of the structure factors. The pre-peak increases intensity with decreasing temperature or adding Ni. Gaussian peaks decomposing radial distribution function (RDF) indicated that Cu-Al distance is anomalously short. These results suggest that a strong interaction between Cu and Al is favorable to form β-phase-like clusters, which leads to chemical medium-range ordering in melt. This promotes formation of order martensite and suppresses γ 2-phase precipitation. The microstructure of the as-spun ribbons was identified by D / Max-rA X-ray diffractometer The order degree of martensite increases with decreasing liquid quenching temperature at the same quenching rate. The liquid structure of Cu 75Al 25 and Cu 71Al 25Ni 4 was investigated using X-ray diffraction method. The distinct pre-peaks have been found in front of main peaks of the structure factors. The pre-peak increases intensity with decreasing temperature or adding Ni. Gaussian peak decomposing radial distribution function (RDF) indicated that Cu-Al distance is anomalously short. These results suggest that a strong interaction between Cu and Al is favorable to form β-phase-like clusters, which leads to chemical medium-range ordering in melt. This promotes formation of order martensite and suppresses γ 2-phase precipitation.