AbstractThis Account describes work by our research group that highlights opportunities to utilize organoboron molecules to direct chemical reactivity in the organic solid state. Specifically, we convey a previously unexplored use of hydrogen bonding of boronic acids and boron coordination in boronic esters to achieve [2+2]-photocycloadditions in crystalline solids. Organoboron molecules act as templates or ‘shepherds’ to organize alkenes in a suitable geometry to undergo regio- and stereoselective [2+2]-photocycloadditions in quantitative yields. We also provide a selection of publications that served as an inspiration for our strategies and offer challenges and opportunities for future developments of boron in the field of materials and solid-state chemistry.1 Introduction1.1 Template Strategy for [2+2]-Photocycloadditions in the Solid State2 Boronic Acids as Templates for [2+2]-Photocycloadditions in the Solid State2.1 Supramolecular Catalysis of [2+2]-Photocycloadditions in the Solid State Using Boronic Acids3 Boronic Esters as Templates for [2+2]-Photocycloadditions in the Solid State3.1 Application of Photoproducts: Separation of Thiophene from Benzene through Crystallization3.2 Crystal Reactivity of B←N-Bonded Adducts: The Case of Styryl­thiophenes4 Conclusions and Perspectives