A　novel　composite　monolithic　column　based　on　graphene　oxide-trimethyl-2-methacroyloxyethylammonium　chloride-titania　(GO-META-TiO2)　was　developed　for　the　enrichment　of　phosphopeptides.　META　was　proposed　as　a　＂bridge＂　to　connect　GO　and　TiO2　species　to　prepare　GO-META-TiO2　composite.　This　high　surface　area　composite　(surface　area　=　196.93　m(2)　g(-1))　was　fixed　in　the　monolithic　column　via　an　in　situ　UV　polymerization　process.　In-tube　solid　phase　microextraction　(IT-SPME)　using　this　composite　was　coupled　with　matrix-assisted　laser　desorption　ionization　time-of-flight-mass　spectrometry　(MALDI-TOF-MS)　for　the　enrichment　and　detection　of　phosphorylated　peptides　from　a　digestion　mixture　of　alpha-casein,　beta-casein,　and　bovine　serum　albumin　(BSA)　in　molar　ratios　of　1:1:1,　1:1:10,　and　1:1:100.　The　key　factors　affecting　the　IT-SPME　of　the　phosphopeptides,　such　as　the　elution　solution　concentrations,　the　extraction　flow　rate,　and　the　elution　flow　rate　were　comprehensively　investigated.　For　further　demonstration,　this　method　was　employed　for　the　enrichment　and　detection　of　phosphorylated　peptides　from　digested　chicken　egg　white.　The　obtained　results　indicated　that　the　GO-META-TiO2　composite　monolithic　column　rapidly　and　efficiently　captured　the　phosphopeptides　present　in　these　complex　biological　samples,　even　in　the　10　fmol　beta-casein　cryptic　digest.　We　therefore　propose　that　the　reported　GO-META-TiO2　composite　monolithic　column　possesses　a　suitable　affinity　for　the　selective　extraction　of　phosphopeptides　from　biological　samples.　This　method　paves　a　way　in　extending　the　application　of　nanomaterials.