AbstractNorbornadiene‐quadricyclane (NBD‐QC) photoswitches are candidates for applications in solar thermal energy storage. Functionally, they rely on an intramolecular [2+2] cycloaddition reaction, which couples the S₀ landscape on the NBD side to the S₁ landscape on the QC side of the reaction and vice‐versa. This commonly results in an unfavourable correlation between the first absorption maximum and the barrier for thermal back‐conversion. This work demonstrates that this correlation can be counteracted by using steric repulsion to hamper the rotational motion of the side groups along the back‐conversion path. It is shown that this modification reduces the correlation between the effective back‐conversion barrier and the first absorption maximum and also increases the back‐conversion entropy. The resulting molecules exhibit exceptionally long half‐lives for their metastable forms without significantly affecting other properties, most notably solar spectrum match and storage density.