The catalytic partial oxidation (CPOX) of several hydrocarbon mixtures, containing n-dodecane (DD), 1,2,4-trimethylbenzene (TMB), and benzothiophene (BT) as a sulfur compound was studied over a Rh/Al2O3 honeycomb catalyst. The in-situ sampling technique SpaciPro was used in this study to investigate the complex reaction system which consisted of total and partial oxidation, steam reforming, and the water gas shift reaction. The mixtures of 83 vol % DD, 17 vol % TMB with and without addition of the sulfur compound BT, as well as the pure hydrocarbons were studied at a molar C/O-ratio of 0.75. The spatially resolved concentration and temperature profiles inside a central channel of the catalyst revealed three reaction zones: an oxidation zone, an oxy-reforming zone, and a reforming zone. Hydrogen formation starts in the oxy-reforming zone, not directly at the catalyst inlet, contrary to methane CPOX on Rh. In the reforming zone, in which steam reforming is the predominant reaction, even small amounts of sulfur (10 mg S in 1 kg fuel) block active sites.