A three-dimensional (3D) structure of multiwalled carbon nanotubes (MWCNTs) interwoven metal–organic frameworks (MOFs) was synthesized. The MWCNTs was utilized to bridge the neighboring MOF nanocrystals. The hybrid material MOFs/MWCNTs was used for SPME coating to extract six PCBS in tea beverages samples by gas chromatography coupled to tandem mass spectrometry. MOFs/MWCNTs coating materials were characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and N2 adsorption–desorption analysis. The response surface method was utilized to systematically optimize the main extraction factors. Under the optimized conditions, the developed method demonstrated wide linear ranges (0.01–1000 ng·L−1), low limits of detection (0.003–0.009 ng·L−1) and high enrichment factors (701–2361) for extracting and determining six PCBS. The six PCBS concentration in environmental tea beverages samples was detected with this method. These results display that MOFs/MWCNTs hybrid materials are potential sorbents in the SPME of PCBS in environmental tea beverages samples.