A novel polyamine-type polystyrene resin with triethylenetetramine functional group was synthesized from polystyrene resin through the acetylation followed by the condensation of triethylenetetramine. Effects of reaction solvent, catalyst, mole ratio of raw materials, time and temperature were discussed. The stability and the adsorption property of the polyamine-type polystyrene resin toward 4-nitrophenol were also studied. The results showed that the complete exchange capacity of the synthesized resin is 4.35 mmol•g-1 when the synthetic reactions take place in 1,2,4-trimethylbenzene by toluenesulfonic acid as catalyst at 160℃ for 20 hours. The equilibrium adsorption capacity of the synthesized resin toward 4-nitrophenol is 192.43 mg•g-1.