By virtue of its long lifespan and outstanding storage intensity with near-zero heat loss, salt hydrate thermochemical energy storage (TES) materials provide a feasible option for the effective use of renewable energy and overcoming its unsynchronized supply and demand. Here, an activated porous carbon originating from the zeolite imidazolate framework (ZHCM) is fabricated and served as the carbon matrix for the LiOH TES material. The as-synthesized Li/ZHCM2-40 not only has excellent storage intensity (maximum 2414.2 kJ·kg⁻¹) with low charging temperature, but also shows great hydration properties stemming from the ultrahigh surface area and hierarchical porous structure of ZHCM2. Besides, this composite material exhibits superior thermal conductivity, while its storage intensity is only attenuated by 10.2% after 15 times of consecutive charge–discharge process, revealing its outstanding cycle stability. And the numerical simulation results also demonstrate its superior heat transfer performance. The developed LiOH TES composite may afford a new avenue for efficient low-grade thermochemical energy storage and liberate the possibility of further exploration of metal organic frameworks derived porous carbon matrix in the future.