Enantiomeric separation of bisoprolol, atenolol, clenbuteral and terbutaline was studied on capillary column using vancomycin as chiral stationary phase by capillary liquid chromatography (CLC) and pressurized capillary electrochromatography (pCEC). Bisoprolol, atenolol, clenbuteral and terbutaline were enantioseparated in the medium of methoanol/isopropanol/triethylamine/acetic acid (60/40/0.05/0.1) with the resolution (Rs) of 1.9, 1.4, 1.1, 0.9 respectively by CLC. The resolution was 1.9, 1.4, 1.5 and 1.5 in polar organic mode by pCEC. And the resolution of bisoprolol, atenolol, clenbuteral was 2.0, 1.7, 1.2 in reversed-phase mode, however, the chiral separation of terbutaline couldn't be achieved. The enantiomeric separation of bisoprolol, atenolol, clenbuteral and terbutaline was successfully achieved in CLC, polar organic pCEC and reversed phase pCEC mode,which revealed the significant complementarity of three modes.