An　efficient　and　stable　adsorbent　is　of　critical　importance　for　solid-phase　microextraction　(SPME).　In　this　study,　we　prepared　metal–organic　framework-derived　nitrogen　(N)-doped　carbon　(C)　nanotube　cages　(N-CNTCs)　with　unique　N-doped　active　sites　and　C-rich　nanotubes　to　coat　SPME　adsorbents.　This　new　material　was　obtained　via　a　simple　thermal　treatment　with　ZIF-67,　and　exhibited　high　porosity　and　excellent　chemical　and　thermal　stability.　Compared　with　commercial　fibers　and　traditional　C　nanotubes-coated　fiber　(15　nm),　N-CNTC-coated　fiber　exhibited　better　extraction　properties,　mainly　due　to　its　π–π　interactions,　abundant　active　sites,　and　hollow　cage　structure,　which　is　composed　of　interconnected　crystalline　N-doped　C　nanotubes.　N-CNTC-coated　fiber　exhibited　better　extraction　performance　and　shorter　extraction　equilibrium　time　than　the　solid　N-doped　C-coated　fiber　due　to　its　hollow　cage　structure.　The　N-CNTC-coated　fiber　was　then　used　to　identify　polychlorinated　biphenyls　(PCBs)　with　wide　linear　range　(0.3–1000.0　ng　L−1),　low　limits　of　detection　(0.10–0.22　ng　L−1),　good　repeatability　(intra-day,　2.6–3.8%;　inter-day,　3.3–4.8%),　and　good　reproducibility　(<8.6%).　We　then　successfully　applied　the　N-CNTC-coated　fiber　to　detect　PCBs　in　river　water　samples　from　six　cities　in　Fujian　Province　and　obtained　satisfactory　recovery　levels.　Thus,　the　novel　N-CNTCs　coating　proposed　in　this　study　is　a　promising　candidate　for　SPME　coating.　©　2019　Elsevier　B.V.