Electrochemical real-time mass spectrometry (EC-RTMS) is a novel technique for the real-time monitoring of gaseous and liquid products of electrochemical reactions, independent of their vapor pressure, with excellent temporal and potential resolution. The scope of this manuscript is to provide details on the interpretation of data for this new technique and on the assignment of mass signals to reaction products by studying three model reactions. The bulk products of the electrochemical oxidation of methanol, ethanol and 1-propanol are characterized by EC-RTMS during potentiodynamic measurements, and the capabilities of the method in detecting reaction products in real time are demonstrated. The importance of proton affinity for the detection of reaction products is highlighted.