A study on zirconium-modified hexaaluminates La0.8ZrxNiAl11O19-delta (x = 0, 0.02, 0.04, 0.06, 0.08, and 0.10) for CO2 reforming of CH4 was carried out. The modifier zirconium improved the catalytic activity, especially the conversions of CH4 and CO2 reached 93.4% and 97.7% over La0.8Zr0.04NiAl11O19-delta. Both the XPS and TPR data indicated the presence of Ni3+ and Ni2+. It was found that the Ni3+/Ni2+ ratio depended upon the amount of the Zr, which facilitated the formation of highly dispersed active Ni-0 species.