N-Heterocyclic carbene (NHC) catalyzed radical-radical reactions have been proven to be powerful strategies for assembling ketyl-containing compounds via single electron transfer (SET) pathway under either thermal conditions or photoredox conditions. In this context, acylation of alkenes via radical relay under NHC-organocatalysis has also opened a new window for the difunctionalization of alkenes to construct valuable molecules in organic synthesis. In this review, the advances and progress of the acylation of alkenes via NHC-organocatalysis were summarized according to different ways of generation of the key NHC-bound ketyl-type radicals. Furthermore, reaction scopes, limitations and mechanisms were discussed based on reaction types and catalytic systems. Conclusions and perspectives were also put forward at the end.