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A dehydroxylative ring-opening Giese reaction of cyclobutanone oximes enabled by photoredox/Ti dual catalysis has been reported in this work. This protocol avoids the prefunctionalization of oximes and the use of stoichiometric triarylphosphine reagents. It also features mild conditions, broad substrate scope and good functional group tolerance. The gram-scale reaction, product derivatization, late-stage functionalization of complex pharmaceutical and natural product derivatives, and oligopeptide modification exhibit the potential application of this methodology in synthetic chemistry.