Natural gas steam reforming (SR) over technically used rhodium/alumina (Rh/Al2O3) honeycomb catalysts is studied experimentally at temperatures between 923 and 1073 K and steam-to-carbon ratios (S/C) of unity, with regard to coke deposition caused by the decomposition of the product species ethylene (C2H4) and carbon monoxide (CO). Furthermore, the process is modeled using detailed reaction mechanisms, and numerical simulations are carried out to describe the coke formation on Rh/Al2O3 catalysts quantitatively. The amount of deposited carbon was detected and analyzed for varying feed mixtures of the products CO and C2H4 diluted in N-2. During the decomposition of CO, the saturation of the amount of coke is monitored by feeding CO in high concentrations. No saturation occurs for the same amounts of coke resulting from the decomposition of C2H4. The coking rate caused by the decomposition of C2H4 is found to be similar to 25 times higher than the coking rate caused by the decomposition of CO. The differences in coking behavior caused by C2H4 and CO, respectively, are described by coking models.