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Constructing a reliable and robust cobalt-based catalyst for hydrogen evolution via hydrolysis of sodium borohydride is appealing but challenging due to the deactivation caused by the metal leaching and re-oxidization of metallic cobalt. A unique core–shell-structured coronavirus-like Co@C microsphere was prepared via pyrolysis of Co-MOF. This special Co@C had a microporous carbon coating to retain the reduced state of cobalt and resist the metal leaching. Furthermore, several nano-bumps grown discretely on the surface afforded enriched active centers. Applied in the pyrolysis of NaBH4, the Co@C-650, carbonized at 650 °C, exhibited the best activity and reliable recyclability. This comparable performance is ascribed to the increased metallic active sites and robust stability.