A　pressure-assisted　CEC　with　ESI-MS　based　on　poly(1-hexadecene-co-trimethylolpropane　trimethacrylate)　monolithic　column　for　rapid　analysis　of　two　beta(2)-agonists　and　three　narcotics　was　established　in　this　article.　After　the　organic　polymer-based　monolithic　column　was　prepared　by　an　in-situ　polymerization　procedure,　a　systematic　investigation　of　the　pressure-assisted　CEC　separation　and　ESI-MS　detection　parameters　was　performed.　Baseline　separation　of　the　studied　analytes　could　be　obtained　using　the　solution　containing　75%　ACN　v/v　and　20　mmol/L　ammonium　acetate　with　pH　8.0　as　running　buffer,　when　applying　separation　voltage　of　20　kV　and　assisted　pressure　of　5　bar.　Under　the　optimized　conditions,　two　beta(2)-agonists　and　three　narcotics　could　be　completely　resolved　and　accurately　determined　within　15　min.　Finally,　the　proposed　method　was　successfully　used　for　real　urine　samples　detection.