An electrochemical study based on direct current (dc) and differential pulse (dp) polarography and coulometry for Folpet, Captan, Captafol and their hydrolyses products was carried out. It was conducted in 10% (v/v) dimethylformamide-water, 0.20 M acetic acid-sodium acetate medium, pH 2.6. The electrochemical behaviour of the fungicides assayed was interpreted according to the polarographic and coulometric data and with the aid of other techniques such as Fourier transform-infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS), that were used to identify the products obtained in the coulometry assays. The possible reduction mechanisms of the electrochemical processes shown by the three fungicides are discussed. Also, different polarographic procedures are proposed for the determination of the fungicides, reporting that it is not possible to perform simultaneous polarographic quantification of the three compounds.