In　this　work,　a　hollow　zirconium-porphyrin-based　metal-organic　framework　(HZ-PMOF)　was　prepared　as　a　coating　for　solid-phase　microextraction　(SPME)　fiber　to　determine　two　naphthols.　HZ-PMOF　coating　provided　good　extraction　performance　for　naphthols　because　of　the　rich　forces　including　π-π　interactions,　hydrogen　bonding,　and　electrostatic　interaction　between　the　materials　and　targets.　Furthermore,　due　to　the　special　shape　of　the　hollow　structure,　HZ-PMOF　coating　showed　time-saving　SPME　equilibrium　time　and　higher　extraction　capacity　than　zirconium-porphyrin-based　metal-organic　framework　(Z-PMOF)　coating　without　hollow　structure.　Combining　with　gas　chromatography-tandem　mass　spectrometry　(GC-MS/MS),　an　analytical　method　of　naphthols　with　low　detection　limit　(1.0　ng　L−1),　wider　linear　range　(3.0–1000.0　ng　L−1)　and　good　reproducibility　(RSD　≤8.6%)　was　established.　Subsequently,　naphthols　in　water　samples　from　five　cities　in　China　were　successfully　detected　by　this　developed　method　with　satisfactory　recoveries　(81.1%–117.9%)　and　precision　(RSDs,　3.2–9.6%).　The　results　indicated　that　the　prepared　HZ-PMOF-coated　fiber　has　good　application　prospects,　and　would　broaden　the　application　of　materials　with　special　morphology　in　the　field　of　pretreatment.　©　2022　Elsevier　B.V.