Allyamine or sodium vinyl sulfate was added into the solutions of acrylamide and N,N′-methylenebisacrylamide to make mixed monomer solutions. These solutions were respectively introduced in methacrylsiloxane-modifidied capillaries. In situ polymerization was initiated by thermally induced radicals. A polymer layer was chemically bonded to the inner wall, resulting in valently modified capillary columns. By altering the addition amounts of allyamine or sodium vinyl sulfate, differently charged polymeric layers were obtained. Five columns were prepared. The result indicated that columns modified with polymers containing amino groups were advantageous over those containing sulphonic acid groups or none. Further comparison revealed that the columns modified with a solution containing 0.15 mol/L acrylamide, 0.03 mol/L N,N′-methylenebisacrylamide and more than 1 mol/L allylamine exhibited good resolution. It is convenient to adjust electroosmotic flows(EOFs) in the columns by this way. In the meantime unspecific protein adsorption was efficiently depressed. When subjected) to zone electrophoresis of proteins from chicken egg white, the column showed high resolution and good reproducibility.