Photochemistry, bearing significant applications in natural and man-made events such as photosynthesis, vision, photolithography, photodynamic therapy, etc., is yet to become a common tool during the synthesis of small molecules in a laboratory. Among other rationale, the inability to influence photochemical reactions with temperature, solvent, additives, etc., dissuades chemists from employing light-initiated reactions as a routine synthetic tool. This review highlights how diverse, highly organized structures such as solvent-free crystals and water-soluble host–guest assemblies can be employed to control and manipulate photoreactions and thereby serve as an efficient tool for chemists, including those interested in synthesis. The efficacy of the media in modifying the excited-state behavior of organic molecules is illustrated with photocycloaddition in general and [2 + 2] photocycloaddition in particular, reactions widely employed in the synthesis of complex natural products as well as highly constrained molecules, as exemplars. The reaction media, highly pertinent in the context of green sustainable chemistry, include solvent-free crystals and solids such as silica, clay, and zeolite and water-soluble hosts that can solubilize and preorganize hydrophobic reactants in water. Since no other reagent would be more sustainable than light and no other medium greener than water, we believe that the supramolecular photochemistry expounded here has a momentous role as a synthetic tool in the future.

Using non-bonding interactions to control photochemical reactions requires an understanding of not only thermodynamics and kinetics of ground state and excited state processes but also the intricate interactions that dictate the dynamics within the system of interest. This review is geared towards a conceptual understanding of how one can control the reactivity and selectivity in the excited state by employing confinement and non-covalent interactions. Photochemical reactivity of organic molecules within confined containers and organized assemblies as well as organic templates that interact through H-bonding and/or cation–carbonyl/cation–π interactions is reviewed with an eye towards understanding supramolecular effects and photocatalysis.