Enzyme mimics emulate the catalytic activities of their natural counterparts. Light-responsive enzyme mimics are an emerging branch of biomimetic chemistry where the catalytic activities can be controlled reversibly by light. These light-responsive systems are constructed by incorporating a suitable photoswitchable unit around the active-site mimic. As these systems are addressable by light, they do not leave back any undesired side products, and their activation–deactivation can be easily controlled. Naturally, these systems have enormous potential in the field of on-demand catalysis. The synthetic light-responsive enzyme mimics are robust and stable under harsh conditions. They do not require special handling protocols like those for real enzymes and can be tailor-made for improved solubility in a variety of solvents. How the introduction of the light-responsive systems has offered a new-edge to the field of small-molecule enzyme mimic has been elaborated in this Mini-review. Recent breakthroughs in light-responsive enzyme-like systems have been highlighted. Finally, the current obstacles and future prospects of this field have been discussed.