This dataset contains data from a study of the electrochemical oxygen reduction reaction (ORR) on zinc hydroxide based model corrosion products electrodeposited on germanium(100). The core of the study is an in situ and operando study of the ORR by attenuated total reflection infrared (ATR-IR) spectroscopy, which is complemented by density functional theory (DFT) calculations. Interpretation relies also on the characterisation of the electrodeposited model corrosion products, which is included here. The following data is included: (i) cyclic voltammograms and ATR-IR spectra recorded during chronoamperometric measurements, (ii) optimised structures and vibrational spectra obtained from DFT calculations of cluster models, (iii) scanning electron micrographs (SEM) of the deposited films before and after electrochemical experiments, including energy dispersive x-ray spectroscopy characterisation of selected samples, (iv) x-ray photoelectron spectra (XPS), and (v) x-ray diffraction data (XRD) of model corrosion products. An absorption at ~1180 cm-1 only in oxygen purged solution indicates the presence of superoxide (hyperoxide) as ORR intermediate. A detailed interpretation of the results, and the experimental details associated with the dataset is available in the associated article.