Difluoromethylene and pyridine cores are very important structural units in medicinal chemistry. Herein, we report the development of photoredox-catalyzed ring-opening and 1,3-alkoxypyridylation of gem-difluorinated cyclopropanes using 4cyanopyrines and alcohols, employing cyclopropane radical cations as the key intermediate. The reaction exhibits high regioselectivity under mild conditions and can also be practiced on gram-scale synthesis, telescoped reaction, and late-stage functionalization of biological molecules.