An　environmentally　friendly　and　sensitive　method　for　determination　of　blockers　and　agonists　was　described　in　this　paper.　The　method　is　based　on　a　homemade　sol-gel　solid-phase　microextraction　(SPME)　coating　with　simultaneous　on-fiber　derivatization　and　subsequent　gas　chromatography　mass　spectrometry　(GC/MS)　analysis.　The　influences　of　the　main　factors　on　the　type　and　thickness　of　the　homemade　fiber　coatings,　conditions　of　the　derivatization,　extraction　and　desorption　of　SPME　were　investigated　in　detail.　The　proposed　procedure　showed　limits　of　detection　lower　than　0.2　ng　mL-1.　The　linearity　was　in　the　0.5-150　ng　mL-1　for　clenbuterol　and　1.0-100　ng　mL-1　for　metoprolol　and　propranolol.　The　variation　in　measurements　(repeatability)　was　below　8.7%　(n=6)　and　the　degree　of　difference　between　(reproducibility)　was　below　11.4%　(n=3).　In　the　application,　spiked　human　saliva　samples　and　real　human　saliva　samples　were　analyzed,　it　was　found　that　saliva　would　affect　the　detection　of　propranolol　when　it　was　a　very　low　content.　The　established　method　can　be　feasible　in　practical　application　and　helpful　for　agonists　and　blockers　preliminary　screening　during　the　competition.　©　2014　Elsevier　B.V.