Abstract: This report focus on phase behavior of polyethylene glycol (PEG)4000/ phosphate/ guanidine hydrochloride/ water system at different guanidine hydrochloride concentrations and pH. The binodal of the systems was displaced toward higher concentrations of the components with increasing guanidine hydrochloride concentrations. The partition coefficient of guanidine hydrochloride was near unity and increased with decreasing pH and increasing PEG/salt (%w/w) ratio.