The C(sp3)–H bond is found widely in organic molecules. Recently, the functionalization of C(sp3)–H bonds has developed into a powerful tool for augmenting highly functionalized frameworks in organic synthesis. Based on the results obtained in our group, the present account mainly summarizes recent progress on the functionalization of C(sp3)–H bonds of aliphatic alcohols, ketones, alkyl nitriles, and ethers with styrene or cinnamic acid using tert -butyl hydroperoxide (TBHP) as a radical initiator. 1 Introduction 2 Oxidative Coupling of Styrenes with C(sp3)–H Bonds 3 Decarboxylative Cross-Couplings of α,β-Unsaturated Carboxylic Acids with C(sp3)–H Bonds 4 Conclusions [ABSTRACT FROM AUTHOR]