The direct selective oxidation of long chain alkanes by O(2) is a highly demanding reaction. We have shown that it is possible to oxidise n-decane in the presence of the oxygen-free radical initiator azobisisobutyronitrile. Formation of a range of oxygenated products has been observed under relatively mild conditions (70 degrees C in air). Although the presence of a catalyst is not essential when the initiator is used, ceria-based catalysts have been found to increase the selectivity to alcohols by modifying the oxyfunctionalisation of decane. (C) 2011 Elsevier Inc. All rights reserved.