We herein presented a mesoporous cellular foam solid-phase microextraction coating that showed highly sensitive recognition for weakly polarity polychlorinated biphenyls in water samples. The mesoporous cellular foam coater fiber was for the first time prepared by a simple sol-gel method. The main experimental parameters including extraction temperature, extraction time, desorption time, stirring rate, and ionic strength were investigated by high-efficiency orthogonal array design, a L16 (44 ) matrix was applied for the identification of optimized extraction parameters, and the optimized method was successfully applied to the analysis of environmental water sample. The novel mesoporous cellular foam coated fibers exhibited sensitive limits of detection (0.07-0.28 µg/L), wide linearity (5-3000 µg/L), and good reproducibility (3.5-8.3% for single fiber, and 4.9-8.7% for fiber-to-fiber) for polychlorinated biphenyls. The home-made coating was successfully used in the analysis of polychlorinated biphenyls in real environmental water samples. These results indicate that the synthesized mesoporous cellular foams are promising materials for adsorption and separation applications in sample pretreatment. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.