Several polyelectrolyte complexes were prepared by the reaction of polyalkylviologens [polyethylviologen (PEV2+), polypropylviologen (PPrV2+), and polybutylviologen (PBV2+) ] with polyanions [sodium alginic (ALG), sodium polyacrylate (PAA), or sodium polystyrenesulfonate (PSS) ]. These complexes were used as electron-transfer catalysts (ETC) on the debromination of diphenyl bromomethane (Ph2CHBr) under heterophase condition [ reductant : Na2S2O4, in H2O (liquid)-polyelectrolyte complex (S)-Ph2CHBr in CH2Cl2]. The work showed that these complexes could induce the debromination of Ph2CHBr to afford tetraphenyl ethane, and different polyanions in the complexes also affected the mediating abilities.