The direct decomposition of H2S into COx-free H-2 and S is an attractive approach in respect of both environmental and energy advantages. However, to achieve the highly effective direct H2S decomposition reaction is a critical scientific challenge, owning to the serious thermal equilibrium limitation in this reaction. Herein, we develop carbon encapsulated Mo2C-Co2C/SiC composite (Mo2C-Co2C/SiC@C) via in-situ microwave carbonization, as a novel microwave catalyst for highly effective direct decomposition of H2S into COx-free H-2 and S by microwave catalysis. Significantly, the H2S conversion is impressively up to 90.3% at 750 degrees C over Mo2C-Co2C/SiC@C microwave catalyst in the microwave catalytic reaction mode, which greatly surpasses the corresponding H2S equilibrium conversion in the conventional reaction mode. Importantly, Mo2C-Co2C/SiC@C exhibits outstanding stability under microwave irradiation. It is found that microwave catalysis can break the chemical equilibrium limitation of the H2S decomposition reaction, which displays a significant microwave selective catalytic effect. This work provides a novel route for high value utilization of toxic and abundant H2S resources, and thus opens a new approach for the design of high active and stable microwave catalysts in microwave catalytic reactions. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.