Electrochemistry and exploiting electrochemical fingerprints is a potent approach to address newly emerging surveillance needs, for instance, for antibiotics. However, a comprehensive insight into the electrochemical oxidation behavior and mechanism is required for this sensing strategy. To address the lack of knowledge of the voltammetric behavior of the cephalosporin antibiotics, a selection of cephalosporin antibiotics and two main intermediates were subjected to an electrochemical study of their redox behavior by means of pulsed voltammetric techniques and small-scale electrolysis combined with HPLC-MS/MS analyses. Surprisingly, the detected oxidation products did not fit the earlier suggested oxidation of the sulfur group to the corresponding sulfoxide. The influence of different side chains, both at the three and seven position of the β-lactam core structure on the electrochemical fingerprint, were investigated. Additional oxidation signals at lower potentials were elucidated and linked to different side chains. These signals were further exploited to allow simultaneous detection of different cephalosporins in one voltammetric sweep. These fundamental insights can become the building blocks for a new on-site screening method.