An emerging strategy in the design of efficient gas storage technologies is the development of stimuli‐responsive physisorbents which undergo transformations in response to a particular stimulus, such as pressure, heat or light. Herein, we report two isostructural light modulated adsorbents (LMAs) containing bis‐3‐thienylcyclopentene (BTCP), LMA‐1 [Cd(BTCP)(DPT)2] (DPT=2,5‐diphenylbenzene‐1,4‐dicarboxylate) and LMA‐2 [Cd(BTCP)(FDPT)2] (FDPT=5‐fluoro‐2,diphenylbenzene‐1,4‐dicarboxylate). Both LMAs undergo pressure induced switching transformations from non‐porous to porous via adsorption of N2, CO2 and C2H2. LMA‐1 exhibited multi‐step adsorption while LMA‐2 showed a single‐step adsorption isotherm. The light responsive nature of the BTPC ligand in both frameworks was exploited with irradiation of LMA‐1 resulting in a 55 % maximum reduction of CO2 uptake at 298 K. This study reports the first example of a switching sorbent (closed to open) that can be further modulated by light. [ABSTRACT FROM AUTHOR]