A first example of low-energy blue-light-mediated formal Doyle-Kirmse reaction for gem-difluoroallylation of aryl diazoesters has been developed. A variety of highly functionalized gem-difluoroallyl containing esters bearing transformable sulfur and bromine groups were efficiently assembled with broad substrate scope under mild, catalyst-free, and additive-free conditions. The reaction represents a practical and environmentally friendly approach for C-CF2 bond formation based on rearrangement strategy, which will find potential applications among drug discovery and development.