An unprecedented N-heterocyclic carbene (NHC)-catalyzed radical acylation of cycloalkyl silyl peroxides was developed using readily available aldehydes as the acylating agents. This protocol provides an exceptionally useful method for the efficient and rapid synthesis of long-chain 1,6-/1,7-/1,8-diketones, especially unsymmetrical ones. This strategy also has the advantages of mild conditions, good functional group compatibility, and potential applications in the late-stage functionalization of aldehydes with bioactive fragments and in the construction of long-chain complex bioactive molecules.