Abstract A facile and scalable spray pyrolysis process is applied to synthesize multi-shelled Ni-loaded yolk-shell catalysts on various supports (Al 2 O 3 , CeO 2 , ZrO 2 , and La(OH) 3 ). The prepared catalysts are applied to direct internal reforming (DIR) in a molten carbonate fuel cell (MCFC). Even on exposure to alkali hydroxide vapors, the Ni-loaded yolk-shell catalysts remain highly active for DIR-MCFCs. The Ni@Al 2 O 3 microspheres show the highest conversion (92%) of CH 4 and the best stability among the prepared Ni-loaded yolk-shell catalysts. Although the initial CH 4 conversion of the Ni@ZrO 2 microspheres is higher than that of the Ni@CeO 2 microspheres, the Ni@CeO 2 microspheres are more stable. The catalytic performance is strongly dependent on the surface area and acidity and also partly dependent on the reducibility. The acidic nature of Al 2 O 3 combined with its high surface area and yolk-shell structure enhances the adsorption of CH 4 and resistance against alkali poisoning, resulting in efficient DIR-MCFC reactions.