Traditional refrigeration technologies based on compression cycles of greenhouse gases pose serious threats to the environment and cannot be downscaled to electronic device dimensions. Solid-state cooling exploits the thermal response of caloric materials to changes in the applied external fields (i.e., magnetic, electric and/or mechanical stress) and represents a promising alternative to current refrigeration methods. However, most of the caloric materials known to date present relatively small adiabatic temperature changes ([Formula: see text] to 10 K) and/or limiting irreversibility issues resulting from significant phase-transition hysteresis. Here, we predict by using molecular dynamics simulations the existence of colossal barocaloric effects induced by pressure (isothermal entropy changes of [Formula: see text] J K[Formula: see text] kg[Formula: see text]) in the energy material Li[Formula: see text]B[Formula: see text]H[Formula: see text]. Specifically, we estimate [Formula: see text] J K[Formula: see text] kg[Formula: see text] and [Formula: see text] K for a small pressure shift of P = 0.1 GPa at [Formula: see text] K. The disclosed colossal barocaloric effects are originated by a fairly reversible order-disorder phase transformation involving coexistence of Li[Formula: see text] diffusion and (BH)[Formula: see text] reorientational motion at high temperatures.