Steam reforming of logistic fuel was conducted at 800oC at atmospheric pressure using n-hexadecane as the surrogate for logistics fuel and thiophene as the source of sulfur. Close examination of the fresh catalyst using transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) revealed the presence of two kinds of active metal particles; one containing Ni and the other containing predominantly Rh. Temperature programmed reduction (TPR) and X-ray diffraction (XRD) confirmed the formation of aluminates of both nickel and rhodium due to high calcinations temperatures. It was observed that sulfur preferentially adsorbs on the surface of nickel particles while protecting rhodium, which remains active for steam reforming. There was no bulk nickel sulfide formation and only surface adsorption was seen. Also, whiskers of carbon were seen in catalysts containing no or very low rhodium content while presence of high rhodium prevented the formation of the same.