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Co-based catalysts are highly active for synthesizing long-chain paraffins through Fischer–Tropsch synthesis. However, their exothermic reactions can cause overheating and catalyst deactivation. To address this, thermally conductive SiC-Al 2 O 3 pellets (HeatPath™) were coated with a Co/Re/Al 2 O 3 shell, significantly boosting the CO conversion rate and the yield of C 2–4 and C 5+ hydrocarbons over a wide range of temperatures by dissipating the reaction heat. The core@shell HeatPath@Co/Re/Al 2 O 3 catalyst demonstrated high productivity (up to 19.7 g CO g cat − 1 h−1), exceptional long-term stability over 660 h time-on-stream, with high-temperature operation up to 260 °C, a low CH 4 selectivity (7.1 %) and a chain growth probability (α) > 0.8. In contrast, the irreversible deactivation of a powder Co/Re/Al 2 O 3 catalyst started at 195 °C, resulting in >60 % CH 4 selectivity and ∼100 % CO conversion due to excessive local heat. The CO conversion rate on the core@shell catalyst could be further improved by increasing the H 2 /CO ratio and temperature, with commercially viable CH 4 selectivity. [Display omitted] • core@shell SiC-Al 2 O 3 @Co-Re showed high performance in Fischer-Tropsch synthesis. • core@shell catalyst improved CO conversion rate and yield of C5 + hydrocarbons. • Heat dissipation property of SiC-Al 2 O 3 pellets enhanced Fischer-Tropsch performance. • Low CH 4 and CO 2 selectivities over a wide temperature range. • High productivity (∼19.7 g CO g cat − 1 h−1) and good stability >660 h time-on-stream. [ABSTRACT FROM AUTHOR]