Abstract: Conventional solar thermochemical heat storage based on indirect surface-heating usually suffers from high heat losses and low solar-chemical efficiency. Here, a different solar thermochemical heat storage system based on direct solar illumination on fluidized black CaCO3 pellets is proposed. A Computational Fluid Dynamics-Discrete Element Method (CFD-DEM) model considering irradiation ray tracing, granular flow, heat and mass transfer, and chemical reaction, is built. Black CaCO3 pellets are fabricated via a facile template mixing method, and the solar absorptance is enhanced to 63.9% from 27.9% of traditional pure CaCO3. Effects of gas velocity and irradiative flux on thermochemical heat storage performance in a fluidized volumetric bed are investigated by incorporating measured kinetic and solar absorptance properties of designed black CaCO3 pellets. The peak solar-chemical efficiency reaches a value higher than 43% benefiting from enhanced solar absorptance, higher gas velocity and irradiative flux. This work guides the design of the high-efficiency direct solar thermochemical heat storage system.