Among the current huge development activities in C–H functionalization, asymmetric oxidative C(sp³)–H bond coupling strategies have remained underrepresented. Beyond the initial examples using chiral metal complexes, the use of organocatalysis provides a new direction for the design of new asymmetric C–H bond cross-coupling reactions. This highlight focuses on the latest advances in metal-free asymmetric oxidative C(sp³)–H bond functionalization using cooperative non-covalent organocatalysis.