AbstractThe development of photoresponsive systems with non‐invasive orthogonal control by distinct wavelengths of light is still in its infancy. In particular, the design of photochemically triggered‐orthogonal systems integrated into solid materials that enable multiple dynamic control over their properties remains a longstanding challenge. Here, we report the orthogonal and reversible control of two types of photoswitches in an integrated solid porous framework, that is, visible‐light responsive o‐fluoroazobenzene and nitro‐spiropyran motifs. The properties of the constructed material can be selectively controlled by different wavelengths of light thus generating four distinct states providing a basis for dynamic multifunctional materials. Solid‐state NMR spectroscopy demonstrated the selective transformation of the azobenzene switch in the bulk, which in turn modulates N₂ and CO₂ adsorption.