In this work, the synthesis of peroxyacetic acid and peroxoacetate salts by electrolysis with conductive-diamond anodes is described, using three different raw materials: ethanol, acetaldehyde, and sodium acetate. Results show that peroxyacetic acid is produced at significant concentrations during the electrolyses of the three raw materials, although sodium acetate achieves the highest efficiency and, at the same time, the smallest carbon mineralization. Acetaldehyde behaves as a good raw material during a first stage but, afterward, it catalyzes the decomposition of peroxoacetate to the acetate anion. Moderate current densities and slightly alkaline pH seems to promote the synthesis of peroxyacetic acid and to restrain raw matter mineralization.