The local atomic structure of an amorphous NiZr2 alloy is identified by using x-ray diffraction, transmission electron microscopy, and differential scanning calorimeter. Based on the experimental results, molecular dynamics simulation is performed to investigate the glass formation of liquid NiZr2 alloy. Some relevant features of the pair correlation functions are in good agreement with those obtained by experiment. The pair analysis parameters are calculated, suggesting that there exist icosahedral ordering, four-fold symmetrical bipyramid and triangularfaced polyhedral units in the amorphous NiZr2 structure. The result is beneficial to open avenues toward the understanding of fundamental theoretical problems of glass formation of simple binary alloys.