Mesoporous yttria-stabilized zirconia (YSZ-X) supports with different Y/Zr molar ratio (X) were prepared by a sol–gel method. 20wt% Ni catalysts supported on YSZ-X (X=0, 0.1, 0.2, and 0.3) were then prepared by an incipient wetness impregnation method for use in hydrogen production by auto-thermal reforming of ethanol. The effect of Y/Zr molar ratio (X) on the catalytic performance of Ni/YSZ-X (X=0, 0.1, 0.2, and 0.3) catalysts was investigated. Hydrogen selectivity and by-product distributions over the catalysts were different depending on the Y/Zr molar ratio (X). Hydrogen selectivity over Ni/YSZ-X (X=0, 0.1, 0.2, and 0.3) catalysts showed a volcano-shaped curve with respect to Y/Zr molar ratio (X). Among the catalysts tested, Ni/YSZ-0.1 showed the best catalytic performance and the lowest carbon deposition in hydrogen production by auto-thermal reforming of ethanol. High reducibility and excellent structural stability of Ni/YSZ-0.1 catalyst were responsible for its superior catalytic performance.