Environment friendly activation and oxidative transformation of C(sp3)-H into value-added compounds by O2 represents a sustainably artificial pathway with excessive atomic financial system and environmentally-friendly options. Nevertheless, each C(sp3)-H and O2 have to be activated successfully, and this can be troublesome to realize with a catalysts that incorporates just one sort of lively website. Herein, the dual-active websites of oxygen emptiness and cobalt species have been constructed within the cobalt-doped nanorods of ceria for respective activation of O2 and C(sp3)-H, enabling an environment friendly oxidative toluene for subsequent Knoevenagel condensation with malononitrile to yield benzylidenemalononitrile underneath gentle situations. In depth experiments and theoretical simulations revealed that the oxidation of C(sp3)-H in toluene to aldehyde intermediates was realized via the spillover of lively oxygen species from oxygen emptiness to cobalt website owing to excessive capability of oxygen mobility within the faulty CeO2. Subsequently, the facile condensation with malononitrile on CeO2 was additionally promoted by the presence of cobalt website. This dual-active website course of supplies an alternate method for the efficient oxidation of C(sp3)-H by O2/air for consequent transformation.