Catalytic autothermal reforming (ATR) of a number of hydrocarbon fuels was studied over composite RhCZ-S catalyst (0.24 wt% Rh supported on structured Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl carrier). Iso-octane and n-hexadecane as model compounds of gasoline and diesel fuel, respectively, showed similar properties in ATR process, indicating weak influence of molecular weight and branching degree of liquid alkanes on catalyst performance. Biodiesel ATR characteristics were similar to those of n-hexadecane ATR, as the utilized biodiesel predominantly contained alkanes, being products of fatty acid tail fragments hydrogenation. Even in the case of gasoline ATR, sufficient amount of monoaromatics did not influence a lot on the catalyst performance. Diesel ATR showed rather different situation: the catalyst tended to lose activity due to coking, and incomplete fuel conversion was observed. Analysis of unreacted fuel revealed bi- and polyaromatic compounds (mainly naphtalenes and antracenes) were difficult to convert.