A newly designed ultrafine NiO-La2O3-Al2O3 aerogel catalyst has been successfully prepared by the combination of sol-gel method and supercritical drying (SCD) technique for CH4/CO2 reforming. Compared to the conventional impregnated catalyst, it exhibits unusual physical and chemical properties, as manifested in very large specific surface area, well-defined pore size distribution and good textural stability. Very high activity and at the same time very low carbon deposition were also observed. It more easily forms homogeneously distributed NiAl2O4 spinel in aerogel catalyst at low heat treatment temperature and has much higher capacity to adsorb CO2, which may be mainly responsible for its excellent catalytic performance and insensitive to carbon deposition.