Direct carbon fuel cells are an attractive alternative for conventional power generation; however, there is almost no information on the stability of conventional fuel cell materials in direct carbon fuel cell environments, in particular when exposed to realistic fuels and the contaminants contained within these fuels. Similarly, there is little information on the structure and phase assemblage of solid fuels exposed to typical environments found in direct carbon fuel cells. In this paper, we use in situ high-resolution synchrotron powder diffraction on conventional high-temperature fuel cell materials and untreated brown coal to assess the stability and reactivity of these materials at various temperatures up to 850Â Â°C. Materials investigated include nickel metal (Ni), gadolinium-doped ceria (GDC) and yttria-stabilised zirconia (YSZ). The phase stability, crystallite size, lattice parameters and associated linear coefficient of thermal expansion were determined. The phase stability of all fuel cell materials was found to be good with no additional phase formation noted either during heating or after prolonged periods at temperature. An increase in the crystallite size was observed for both GDC and Ni. Non-linear thermal expansion observed in these materials was related to partial reduction of cerium ions (GDC) and due to a Curie point transition (Ni). A wide range of mineral phases were observed in the coal samples and these phases were found to change significantly with temperature. Mineral phases consistent with the ash composition and existing literature on Victorian brown coal were assigned to phases observed.