We report a photoredox-catalyzed, redox-neutral [3+2] annulation of cyclopropanols with electron-deficient alkenes that integrates proton-coupled electron transfer (PCET) activation and a radical-polar crossover sequence within a single catalytic cycle. PCET oxidation of cyclopropanols generates β-keto radicals, which add to activated alkenes and undergo single-electron reduction to form carbanion intermediates, enabling intramolecular aldol-type cyclization to furnish densely substituted cyclopentanols under mild conditions. Dehydroalanine derivatives serve as particularly effective partners, delivering cyclic α,α-disubstituted amino-acid and peptide derivatives with high diastereoselectivity while accommodating primary, secondary, and tertiary radical precursors. Acrylates, acrylonitriles, maleimides, and 1,1-diarylethylenes are also compatible substrates. This redox-neutral catalytic platform expands the synthetic utility of cyclopropanols as ambiphilic three-carbon building blocks, enabling streamlined access to functionalized five-membered carbocycles.