Currently, about 80 pet. of hydrogen is produced from natural gas alone by Steam Methane Reforming (SMR), Partial Oxidation (POX) and Autothermal Reforming (ATR) in the form of syngas which is mainly a mixture of hydrogen and carbon monoxide. Produced hydrogen is predominantly used to manufacture basic chemicals such as ammonia and methanol and to upgrade petroleum products and oils in refining processes. Gasification of coal and other heavy hydrocarbons is also a viable technology for syngas production. There are many corrosion related materials challenges in industrial processes for syngas production from fossil fuels. This paper examines these challenges with particular emphasis on a high temperature material degradation phenomenon termed "metal dusting" which is a severe form of corrosion involving the break up of a bulk metallic structure into powder or "dust" consisting of metal particles, oxides and carbides. Control strategies to combat this form of corrosion are also outlined. Also included are materials challenges related to ExxonMobil's advanced steam reforming process known as Pressure Swing Reforming (PSR). This technology is a new way to make syngas from gaseous as well as liquid hydrocarbons and can be utilized in different process scenarios ranging from on-board vehicle reforming to industrial syngas production.