In recent years, the use of vanadium complexes as catalysts and air or oxygen as oxidants has emerged as a new method for the effective oxidative carbon–carbon bond cleavage in a series of substrates, including 1,2-diols and α-hydroxy ethers. In addition to the advantageous use as a synthetic tool, vanadium catalyzed aerobic CC bond cleavage becomes even more appealing if applied to the degradation of lignocellulosic biomass and in particular in the oxidative depolymerization/degradation of lignin or cellulose. In this review, this chemistry, the most recent advances and the role played by homogeneous vanadium complexes are presented and discussed.