Ce0.5Zr0.5O2 supported Ni-based catalysts with a Ni loading of 10 wt% and a B loading of 0.5 wt% were prepared by co-precipitation (assigned as NiCeZr(C) and BNiCeZr(C), respectively) and impregnation (assigned as NiCeZr(I) and BNiCeZr(I), respectively) procedures to evaluate the effects of fabrication methods and B-doped on the catalytic performance for steam reforming of ethanol (SRE). These catalysts were characterized with XRD, TPR, TPO, TEM, BET, TG and EA. The well dispersed active species that can be obtained through co-precipitation and formation of a Ni–B alloy come from a B-doped catalyst, which can promote catalysis performance and reaction pathway. Further, it can improve the selectivity of hydrogen for a SRE reaction. Also, the B-doped catalysts possess a high oxygen storage capacity (OSC) via formation of CeBO3 under SRE ambience, which is the factor for removal of the carbonaceous species. TG and EA analyses demonstrate that there are fewer carbon deposits for the B-doped catalysts. The performance of the BNiCeZr(C) catalyst was preferential among these catalysts.