Monoliths were prepared by different polymerization techniques in the present work which were atom transfer radical (ATRP) polymerization (MA), reversible addition-fragmentation chain transfer (RAFT) polymerization (MR) and normal in-situ radical polymerization MI.The results showed that MA had better permeability, larger pore volume and larger pore size than MR and had more uniform structure than MI.The monoliths were used as HPLC stationary phases to separate immune globulin (IgG) from human plasma.The results showed that monoliths prepared by ATRP and RAFT both can be used as HPLC stationary phases to separate IgG from human plasma, in which MA (Fig.1) showed lower back pressure and higher resolution than MR (Fig.2a) and possessed the better character.The monolith MI (Fig.2b) had no ability to separate IgG from human plasma.