In the study presented herein, the catalytic activity and stability of a Ni catalyst supported on Y2O3–ZrO2 was examined for the first time in the glycerol steam reforming reaction and compared with a Ni/ZrO2. The addition of Y2O3 stabilized the ZrO2 tetragonal phase, increased the O2 storage capacity of the support and the medium strength acid sites of the catalyst, and although the Ni/Zr catalyst had a higher concentration of basic sites, the Ni/YZr presented more stable monodentate carbonates. Moreover, the Ni/YZr had substantially higher Ni surface concentration and smaller Ni particles. These properties influence the gaseous products’ distribution by increasing the H2 yield and selectivity and preventing the transformation of CO2 to CO, by inhibiting the reverse water gas shift (RWGS) reaction from taking place. For both catalysts the main liquid products identified were allyl alcohol, acetaldehyde, acetone, acrolein, acetic acid and acetol; these were subsequently quantified. The time-on-stream experiments showed that the Ni/YZr was more stable during reaction and had a higher H2 yield after 20 h (2.17 in comparison to 1.50 mol H2/mol C3H8O3, for the Ni/Zr). Extensive investigation of the carbon deposits showed that although lower amounts of coke were deposited on the Ni/Zr catalyst, these structures were more graphitic in nature and had fewer defects, which means they were harder to oxidize. Moreover, transmission electron microscopy (TEM) analysis showed that sintering of Ni nanoparticles during the reaction was significant for the Ni/Zr catalyst, as the mean particle diameter increased from an initial value of 48.2 to 67.9 nm, while it was almost absent on the Ni/YZr catalyst (the mean particle diameter increased from 42.1 to 47.4 nm). •Y2O3 stabilizes the tetragonal ZrO2 and improves reducibility.•Y2O3 leads to higher Ni surface concentration and smaller Ni particles.•Y2O3 prevents Ni sintering and forms carbon with low crystallinity.•Ni/YZr reveals increased H2 yield, CO2 selectivity and high H2/CO ratio.•Ni/YZr more resistant to deactivation in comparison with the Ni/Zr.