A porous composite adsorbent was developed for miniaturized sample preparation of trace polycyclic aromatic hydrocarbons (PAHs) from environmental waters. A porous composite adsorbent of iron–carboxylate metal-organic frameworks and hypercrosslinked polymer entrapped in gelatin cryogel and coated onto cellulose acetate fibers was fabricated and employed as the solid phase of an in-syringe solid-phase extraction. The adsorption materials can adsorb PAHs through π-π interaction and integrating them could strongly enhance the interaction. The adsorbent was placed into the needle hub and combined with a disposal syringe as an in-syringe extraction device. The porous composite absorbent was characterized, and extraction conditions were optimized to achieve the best extraction performance. Ultra-high performance liquid chromatography with fluorescence detector was utilized to separate and quantify extracted PAHs. The developed analysis method provided a linear of 0.020–50 µg/L for phenanthrene and benzo(b)fluoranthene, 0.010–50 µg/L for pyrene, 0.0020–50 µg/L for benzo(a)anthracene and 0.0050–50 µg/L for benzo(a)pyrene and dibenzo(a,h)anthracene, respectively. The limits of detection ranged from 2.0 to 20 ng/L. Satisfactory recoveries ranged 89 to 98% with RSDs below 7%. The fabricated composite adsorbent had good stability allowed efficient extraction recovery up to 21 cycles of use. This adsorbent also has potential to extract and determine other aromatic compounds from different matrices.