A　novel　open　tubular　(OT)　column　covalently　modified　with　hydrophilic　polysaccharide,　carboxymethylchitosan　(CMC)　as　stationary　phase　has　been　developed,　and　employed　for　the　separations　of　basic　proteins　and　opium　alkaloids　by　capillary　electrochromatography　(CEC).　With　the　procedures　including　the　silanization　of　3-aminopropyltrimethoxysilane　(APTS)　and　the　combination　of　glutaraldehyde　with　amino-silylated　silica　surface　and　CMC.　CMC　was　covalently　bonded　on　the　capillary　inner　wall　and　exhibited　a　remarkable　tolerance　and　chemical　stability　against　0.1　mol/L　HCl,　0.1　mol/L　NaOH　or　some　organic　solvents.　By　varying　the　pH　values　of　running　buffer,　a　cathodic　or　anodic　EOF　could　be　gained　in　CMC　modified　column.　With　anodic　EOF　mode　(pH　＜　4.3),　favorable　separations　of　basic　proteins　(trypsin,　ribonuclease　A,　lysozyme　and　cytochrome　C)　were　successfully　achieved　with　high　column　efficiencies　ranging　from　97,000　to　182,000　plates/m,　and　the　undesired　adsorptions　of　basic　proteins　on　the　inter-wall　of　capillary　could　be　avoided.　Good　repeatability　was　gained　with　RSD　of　the　migration　time　less　than　1.3%　for　run-to-run　(n　=　5)　and　less　than　3.2%　for　day-to-day　(n　=　3),　RSD　of　peak　area　was　less　than　5.6%　for　run-to-run　(n　=　5)　and　less　than　8.8%　for　day-to-day　(n　=　3).　With　cathodic　EOF　mode　(pH　＞　4.3),　four　opium　alkaloids　were　also　baseline　separated　in　phosphate　buffer　(50　mmol/L,　pH　6.0)　with　column　efficiencies　ranging　from　92,000　to　132,000　plates/m.　CMC-bonded　OT　capillary　column　might　be　used　as　an　alternative　medium　for　the　further　analysis　of　basic　proteins　and　alkaline　analytes.　(C)　2010　Elsevier　B.V.　All　rights　reserved.