The purpose of this laboratory study was to investigate the simultaneous impacts of the electro-dewatering process on dry solids (DS) content and mobilization of metals in sewage sludge. The results suggested that the use of polyelectrolytes is necessary in mechanical pressure-driven dewatering and also in electro-dewatering. With polyelectrolyte conditioning, the DS content in the final sludge cake could be increased to 39%. Dewatering with slightly cationic polymer was not effective, but medium, strongly and very strongly cationic polymers performed equally. During electro-dewatering, an increase of voltage from 10 to 40 V resulted in a dryer sludge cake. Polyelectrolyte addition reduced the content of exchangeable metal species and increased less mobile, reducible species in the sludge. Furthermore, the more stable or immobile metal fractions were more likely to remain intact in dewatered sludge. Among heavy metals, Cu and Pb were immobile but Cr, Co, Ni, and Zn could more easily be mobilized during electro-dewatering. The application of high voltage had a direct effect on the migration of metal fractions, whereas, the sludge conditioning by a different cationic polymer had an indirect effect on the migration of these metals during electro-dewatering.