A series of new 6-methyl-2-vinylpyridinium water soluble cationic poly-electrolytes were synthesized with Cl-, Br-, HSO4-, H2PO4-, and NO3- as counter ions and were characterized by UV-visible, NMR, FTIR, and mass spectral studies. The intrinsic viscosity, electrical conductivity, and charge density of the polyelectrolytes were also determined. The effect of counter ion on flocculating ability of polyelectrolytes was investigated with tannery effluent at different concentrations (10-200 ppm). The total suspended solids (SS), COD and BOD, were determined for supernatant solutions to ascertain the extent of flocculation. The flocculating ability was found to be directly proportional to the concentration of the polyelectrolytes.