A　novel　hybrid　affinity　monolith　with　a　high　aptamer　coverage　density　was　developed　via　a　highly　efficient　modification　of　aptamer@gold　nanoparticles　(Apt@AuNPs)　on　a　well-controlled　3D　skeletal　POSS-polyethylenimine　(PEI)　matrix.　The　effects　of　amine　reagents　and　the　skeletal　structures　of　the　hybrid　monoliths　on　the　modification　efficiency　of　Apt@AuNPs　were　studied,　and　the　resultant　Apt@AuNPs@POSS-PEI1200　monolith　was　proposed　with　a　high　coverage　density　of　aptamer　of　up　to　1413　pmol　μL-1,　which　is　4-5　times　more　than　the　coverage　density　when　modified　with　Apt@AuNPs　that　was　reported　previously.　Characterization　including　morphology,　spectra　analysis,　mechanical　stability,　binding　capacity　and　specificity　studies　was　also　carried　out.　Significant　specific　recognition　targeting　of　ochratoxin　A　(OTA)　was　achieved　with　a　detection　limit　as　low　as　0.06　ng　mL-1.　High　recoveries　of　OTA　were　achieved　of　92.6　±　1.3%　to　94.7　±　1.4%　(n　=　3),　while　the　cross-reactivity　towards　analogues　such　as　ochratoxin　B　(OTB)　and　aflatoxin　B1　(AFB1)　was　weak.　This　highlights　a　facile　approach　to　POSS-based　affinity　monoliths　with　a　high　aptamer　coverage　density　for　sensitive　and　selective　recognition　of　a　trace　target　(OTA).　©　2018　The　Royal　Society　of　Chemistry.