Advancements in photocatalysis have enabled access to previously inaccessible intermediates, and have allowed for the development of innovative strategies for bond-formation. These investigations demonstrate that sulfamate esters and sulfamides react productively under photochemical conditions. Sulfamate esters and sulfamides engage in photochemical oxidation to generate nitrogen-centered radical intermediates, which are capable of guiding site-selective alkylation reactions. Sulfamyl and sulfamidy radical intermediates offer complementary site-selectivity for C–H functionalization by participating in 1,6-hydrogen atom transfer (HAT) processes, as opposed to the traditional selectivity arising from 1,5-HAT processes achieved by amide, carbamate, and sulfonamide radical intermediates. Additionally, sulfamate esters and sulfamides can be employed as non-traditional nucleophiles in photochemically-driven, nickel-catalyzed cross-coupling reactions. Photochemical reaction platforms offer user-friendly methods to improve access to underexplored arylated sulfamate ester and sulfamide small molecules.