Chromium-based metal-organic frameworks MIL-101 and MIL-100 catalyzed oxidation of propylene glycol (PG) using tert-butyl hydroperoxide (TBHP) as oxidant. The main oxidation product was hydroxyacetone (HA) while minor oxidation products were acetaldehyde and acetic acid. The best results (88% selectivity toward HA at ca. 10% PG conversion) were achieved over MIL-101 using acetonitrile as solvent. In water, C-C bond cleavage products predominated. MIL-101 and MIL-100 revealed different behavior toward adsorption of PG from MeCN solution, which affected their catalytic performances. Additives of radical chain scavengers produced a strong rate-inhibiting effect whereas the presence of molecular oxygen accelerated the reaction, suggesting radical chain mechanism of the oxidation process. The oxidation of PG over MIL-101 at 50 degrees C proceeded without leaching of the active metal into solution and the catalysis had the truly heterogeneous nature. The MIL-101 catalyst could be recycled without significant loss of activity and selectivity and preserved its structure during, at least three, catalytic cycles. (C) 2016 Elsevier B.V. All rights reserved.