A novel approach for the synthesis of monofluoroalkenes through photocatalyzed decarboxylative/deboronative coupling has been established, utilizing α-fluoroacrylic acids and alkyl trifluoroborates. This methodology provides an efficient strategy to forge C (sp2)–C (sp3) bonds, enabling the transformation of alkyl boron compounds into valuable monofluoroalkenes. The method demonstrates broad substrate scope, accepting a variety of α-fluoroacrylic acids, and yields the sought-after monofluoroalkene products with outstanding Z-selectivity under mild conditions.