The polymerization of acrylamide (AAm) was carried out with a potassium permanganate-Titriplex VI redox initiator system with and without electrolysis. Because of the high metal-ion concentration in general, low-molecular-weight polymers were obtained (weight-average molecular weight = 2600-4000). The effect of potassium permanganate and AAm concentrations and temperature on the polymerization yield was studied and compared with results obtained under the same experimental conditions used for electrolysis. The results of Fourier transform infrared spectroscopy, atomic absorption spectrometry, and scanning electron microscopy (SEM) results are given. SEM micrographs of the polymer obtained by electrochemical methods exhibited smoother surfaces than those obtained by nonelectrolytic methods. In the absence of potassium permanganate, there was no polymerization under experimental conditions. A possible reaction mechanism is suggested. The electro-induced system resulted in about a 50% increase in the yield. Manganese content in the electro-induced and chemical polymerization systems were 2.7 and 8.2%, respectively, supporting the yield increase in the electro-induced system. A graphite electrode was used and resulted in a high yield and a fibrous polymeric structure.