A catalytic methodology for the oxidative cleavage of vicinal diols is described as an advantageous alternative in terms of the environmental impact on classical methods involving toxic oxidants. The novel strategy is based on the use of dioxomolybdenum(VI) complexes as catalysts and dimethyl sulfoxide (DMSO) as an oxidant and displays high selectivity and a broad scope for glycol cleavage. In addition, the developed system is also useful for the oxidation of acyloins to diketones.