<p>The ring-opening functionalization of strained rings represents a highly valuable transformation. However, existing strategies predominantly focus on ring-opening difunctionalization, as initial derivatization typically diminishes the reactivity of surrounding C–H bonds. Consequently, the selective control over site, regio and oxidation state among multiple inert C–H/C–C bonds remains a major unmet challenge. Here we report a multisite programmable, divergent ring-opening functionalization of strained rings via electro-oxidation of continuous C–C bond and multiple C(<i>sp</i>³)–H bonds. The key to this strategy is the generation of olefins through a controlled ‘olefin slow-release pool’, which ensures sufficient selectivity oxidation and suppresses undesired polymerization. Specifically, precise trioxygenation, tetraoxygenation and trihalohydroxylation have been realized, accompanied by controllable remote alkenylation via direct current electrolysis, rapid alternating polarity electrolysis and electrophotocatalysis. This versatile method enables facile transformation of readily accessible strained rings into diverse multi-oxygenated scaffolds, including oxazolines, polyols, polyhalogenated alcohols, as well as bicyclic frameworks via skeletal editing.</p><p></p>