The　occurrence　of　microcystins　(MCs)　during　harmful　algal　blooms　(HABs)　represents　a　major　threat　to　freshwater　environments.　In　this　work,　a　novel　surface　amphiphilic　hybrid　porous　polymers　based　on　cage-like　organosiloxanes　(PCSs)　was　prepared　for　the　enrichment　of　MCs.　The　copolymerization　of　bifunctional　amphiphilic　monomers,　2-methacryloyloxyethyl　phosphorylcholine　(MPC)　and　N-benzylquininium　chloride　(BQN),　with　the　cross-linker　methacryl　substituted　polyhedral　oligomeric　silsesquioxane　(POSS)　was　achieved　in　an　ionic　liquid-based　porogenic　medium.　The　hierarchical　porous　structure,　a　variety　of　surface　functional　groups　and　weak　hydrophilicity　were　well　characterized　on　the　prepared　materials　using　scanning　electron　microscopy,　nitrogen　adsorption/desorption　analysis,　Fourier　transform　infrared　spectroscopy,　X-ray　photoelectron　spectroscopy,　zeta　potential　analysis　and　water　contact　angle　testing,　respectively.　The　as-prepared　surface　amphiphilic　PCSs　was　used　as　an　adsorbent　for　pipette　tip　solid-phase　extraction　(PT-SPE)　to　enrich　microcystins　(MCs)　from　surface　waters　before　their　analysis　by　capillary　electrochromatography　(CEC)　and　liquid　chromatography-mass　spectrometry　(LC-MS).　Under　the　optimal　conditions,　the　established　PT-SPE-LC-MS　method　exhibited　a　wide　linear　range　(10–10,000　ng　L−1),　low　limits　of　detection　(4.0–8.0　ng　L−1)　and　satisfactory　recoveries　(89.5–102.8　%)　for　MCs.　An　adsorption　mechanism　involving　electrostatic　interactions,　hydrogen　bonding,　hydrophilic　interactions,　and　π-π　stacking　has　been　proposed.　The　findings　suggest　that　the　use　of　surface　amphiphilic　PCSs　materials　as　adsorbents　in　the　PT-SPE　platform　facilitates　efficient　enrichment　of　MCs　for　subsequent　chromatographic　analysis.　These　investigations　offer　a　new　perspective　on　the　simple　and　uncomplicated　pretreatment　of　complex　environmental　samples.　©　2024