Polarographic reduction of 2-amino-4-aryl-5-phenylazothiazoles takes place in a single 2-electron transfer, giving a diffusion-controlled irreversible wave in the pH range 2.0-10.0. Substituents in the 4-position of the thiazole moiety shift the half-wave potential through conjugation of the system. A correlation of E(sol;1 2 ) with the Brown and Hammett substituent constant has also been established.