The asymmetric α-amination of 4-substituted pyrazolones with azodicarboxylates was investigated for the first time, employing an N,N'-dioxide gadolinium(III) complex as the catalyst. The novel transformations exhibited high yield, and 4-amino-5-pyrazolone derivatives bearing a chiral quaternary center were obtained in excellent yields (up to 99%) and enantioselectivities (90%-97% ee) for a broad scope of 5-pyrazolones by using 1 mol % or only 0.05 mol % of catalyst.