Using a combined spectro-electrochemical DEMS/ATR-FTIRS set-up, we have investigated the adsorption/oxidation of glycerol on a Pt thin film electrode by potentiodynamic, potentiostatic, and adsorbate-stripping experiments. The potential and time dependent development of the glycerol adlayer was followed by highly surface sensitive in situ ATR-FTIR spectroscopy, while the volatile products formed during the glycerol adsorption/oxidation process were simultaneously monitored by online differential electrochemical mass spectrometry (DEMS). For the assignment of the detected glycerol adsorbates, comparative experiments were carried out, investigating the adsorption/oxidation of glyceraldehyde and glyceric acid. The data show that (i) during the adsorption/oxidation of glycerol, CO(ad) is formed in the potential range between 0.1 and 0.7 V(RHE), which can be oxidized further to CO(2) at potentials above 0.5 V, that (ii) beside CO(ad), adsorbed glycerol (at 0.3 and 0.4 V) and glycerate (between 0.6 and 0.9 V) are formed, that (iii) glyceric acid is a dead end in the electrochemical oxidation of glycerol, and that (iv) glyceraldehyde is an intermediate to CO(ad) formation. (C) 2011 Elsevier B.V. All rights reserved.