AbstractSeveran organic peroxides were studied by differential pulse polarography (DPP) in water and water–solvent media, and compared to hydrogen peroxide. Reduction occurred usually between −0.1 and +0.3 V vs. SCE, except for the peroxides containing atert‐butyl group adjacent to the OO function. In this case, reduction was more difficult and was shifted to the −0.9 to −1.1 V vs. SCE range. Diffusion coefficients were determined and are in the 4 − 9 × 10−10m2s−1range. The detection limits are generally no lower than 5 × 10−5mol l−1, due to the high irreversibility of the reduction process. Calibration plots from 5 × 10−5to about 5 × 10−4m