The polarographic behaviour of the α-arylhydrazonomesoxalonitrile derivatives (IIb-i) and of 2-arylhydrazono-3-keto-3-phenylpropionitriles (IIIb-f) was investigated. With the exception of the nitro-substituted derivatives IIh, i and IIIf all the investigated compounds showed polarographic waves similar to that of their respective parent compounds IIa and IIIa. The m-nitro derivatives IIh and IIIf were firstly reduced in a 4 e wave to the corresponding hydroxylamino derivatives which were subsequently reduced in the manner common to other α-arylhydrazononitriles. On the other hand, the p-nitro derivative IIi was first reduced to the hydroxylamino derivative which then lost water to yield the corresponding quinoneimine. Reduction of the latter product in a 2 e wave gave the p-amino derivative IIe, which then underwent 4 e reduction to p-phenylenediamine and aminomalonitrile. The E 1/2 values corresponding to reduction of the arylhydrazonic moiety of compounds IIa-i and IIIa-f at different pH values were correlated to Hammett's different sigma sets. Analysis of the results provided evidence for the suggested mechanism for reduction of these compounds.