Steam reforming of glycerin on Ni-loaded catalyst was performed using a ZrO2-based support material. The addition of CaO to ZrO2 improved the catalyst performance, and NiO/CaO-ZrO2 afforded glycerin conversion of 88.9% with an H-2 yield of 75.3% at 600 A degrees C. Carbon formation decreased from 4.2 to 2.0% with CaO-added catalyst. Solid solution was formed with the addition of CaO to ZrO2, and it exhibited basic characteristics. Further reduction of carbon formation during the reforming reaction was achieved by using a quaternary complex oxide catalyst NiO-CeO2/CaO-ZrO2, where glycerin conversion of 96.1% and a H-2 yield of 83.7% were achieved with carbon formation of 0.7% at 600 A degrees C.