Design of viable catalysts that exhibits high catalytic activity and stability, as well as resistance against deactivation could be achieved by selecting the right active metal and support, understanding their structure, synergy or the metal support interaction and by employing the right preparation technique. Numerous studies and reviews have dealt with various aspects of CeO2 based catalysts, with the sole target of understanding its activity in various reactions such as dry and steam reforming of methane. Good metal dispersion on CeO2 surface is explained to be the reason for the promising activity of this systems. This review focuses on the synthesis, characterization and application of some CeO2 doped/supported catalysts in hydrogen production by dry and steam reforming of methane, and other reactions. Various synthetic methods for the preparation of the metal doped/supported CeO2 catalysts were introduced with a focus on how to effectively produce stable and efficient catalysts. Subsequently, some advanced characterization techniques were presented to precisely probe the metal and CeO2 at the atomic level, which is critical in investigating the structure of the catalysts.