The homogeneous catalytic system composed of the aqua-soluble tetracopper(II) triethanolaminate complex [O subset of Cu-4{N(CH2CH2O)(3)}(4)(BOH)(4)][BF4](2) (1), t-BuOOH (TBHP), water and acetonitrile solvent (optional) has been applied for the mild oxidation of (i) linear and cyclic alkanes to the corresponding alkyl peroxides, alcohols and ketones, (ii) secondary or primary alcohols to ketones or aldehydes, respectively and (iii) glycerol (GLY) to dihydroxyacetone (DHA). Unusual regio-, bond and stereoselectivity parameters have been determined for the alkane oxygenations and discussed in terms of possible steric, hydrophobic and electronic effects. In alcohol oxidations, secondary alcohols are the most reactive substrates. Yields and TONs up to 82% and 1200, respectively, have been obtained in the oxidation of isopropanol to acetone. The selective oxidation of GLY to DHA by the 1/TBHP system has been also achieved, although providing lower conversions. The 1/H2O2 system for the GLY oxidation is particularly advantageous in terms of selectivity and oxidant efficiency. These systems constitute one of the first examples of a metal-catalyzed oxidation of glycerol under homogeneous conditions. (C) 2010 Elsevier Inc. All rights reserved.