Polyelectrolyte with a large number of cations or anions could precipitate the oppositely charged proteins to form polyelectrolyte-protein complexes, which then aggregated to form larger particles via electrostatic attraction or hydrophobic interaction. The precipitation was affected by the molecular weight and concentration of the polyelectrolyte as well as the ionic strength and pH of the solution. The use of precipitation is an efficient method for selective separation of proteins from crude biological mixtures in the downstream processes of bioengineering.