The reactivity pattern of a model MnCeOx catalyst (Mn-at:Ce-at, 1) in the wet air oxidation (CWAO) of toxic (phenol) and refractory (acetic, oxalic and formic acids) organic pollutants has been probed, using a stirred batch reactor with continuous oxygen feeding (Po-2, 0.9 MPa). In the range of 110-150 degrees C the MnCeOx catalyst (w(cat)/w(sub), 6) shows high abatement and mineralization efficiency toward all the substrates. Parallel trends of substrate and total organic carbon (TOC) conversion prove that adsorption is the primary reaction step, while slower mineralization rates signal that surface oxidation is rate determining step (r.d.s.). Activity data in the pH range of 3-10 and straight relationships between conversion and dissociation constant (K-a) signal that acids adsorption is driven by electrostatic interactions with acid sites (E-Ads approximate to 80 kJ/mol), while a low energetic barrier (E-Ads approximate to 16 kJ/mol) discloses the physical nature of phenol adsorption. A kinetic analysis of conversion-selectivity data, based on a dual-site Langmuir-Hinshelwood (L-H) mechanism, sheds light into the CWAO pattern of MnCeOx catalyst toward different classes of organic pollutants. (C) 2013 Elsevier B.V. All rights reserved.