Vinylboronates and alkylboronates are key components in variegated transformations in all aspects of chemical science. This work describes a sequential radical difunctionalization strategy for the construction of fluorine-containing vinylboronates and alkylboronates with the integrated redox-active reagent N-trifluoromethylthiophthalimide. This multifunctional N-S precursor offers a scalable and practical protocol for the trifluoromethylthiolation-borylation of unsaturated hydrocarbons in a highly regio- and stereoselective fashion, which can be further converted into valuable synthons via boryl migration.