A copper(I)-promoted cycloalkylation-peroxidation strategy has been developed via a three-component reaction involving cycloalkanes, tert-butyl hydroperoxide (TBHP) and internal conjugated alkenes possessing electron-withdrawing groups (EWGs). This process installs C-O and C-C bonds via sp(3) C-H functionalisation with concomitant generation of two stereocentres. This regioselective radical addition of coumarin system is opposite to that of styrene.