AbstractToday, around 20% of the electric consumption is devoted to refrigeration, while around 50% of the final energy is dedicated to heating applications. In this scenario, many cooling devices and heat‐pumps are transitioning towards the use of CO₂ as an eco‐friendly refrigerant, favouring carbon circular economy. Nevertheless, CO₂ still has some limitations, such as large operating pressures (70‐150 bar) and a critical point at 31 °C, which compromise efficiency and increase technological complexity. Very recently, we have reported an innovative breathing‐caloric mechanism in the MIL‐53(Al) compound, which implies gas adsorption under CO₂ pressurization boosted by structural transitions, and which overcomes the limitations of stand‐alone CO₂. Here, we report the breathing‐caloric‐like effects of MOF‐508b, surpassing by 40% those of MIL‐53(Al). Moreover, we present the first thermometry device operating at room temperature and under the application of only 26 bar of CO₂. Under those conditions, our material presents values of ΔT ∼ 30 K, reaching heating temperatures of 56 °C and cooling temperatures of ‐10 °C, which are already useful for space heating, air‐conditioning, food refrigeration and freezing applications.This article is protected by copyright. All rights reserved