The reduction of several o,o'-dihydroxyazo-compounds is studied by means of pulse polarographic techniques (DPP, NPP and RPP). The compounds studied are the following: 2-(2'-hydroxyphenylazo)-phenol (o,o'-dihydroxyazobenzene), 1-(2'-hydroxy-1'-naphthylazo)-2-naphthol-4-sulphonic acid (calcon or Eriochrome Blue Black R), 1-(2'-hydroxy-4'-sulpho-1'-naphthylazo)-2-hydroxy-3-naphthoic acid (calcon carboxylic acid), and 1-(1'-hydroxy-2'-naphthylazo)-6-nitro-2-naphthol-4-sulphonic acid (Eriochrome Black T). Correlations between Ip and Epand experimental variables (pH, T, conc.) and instrumental parameters (dropping time, t, and pulse magnitude, ΔE) are established. Reaction mechanisms formerly proposed are discussed on the basis of the new obtained results, and the ranges are defined where adsorption and/or acid-base catalysis are operative.