Specific separation and extraction is a pivotal stage in the accurate quantification of liquid crystal monomers (LCMs) pollutants in complex environmental samples. In this context, a new fluorinated imprinted adsorbent (MIA) for magnetic solid phase extraction (MSPE) was one-pot prepared within 3.5 h using 4-[difluoro(3,4,5-trifluorophenoxy)methyl]-3,5-difluoro-4'-ethyl-biphenyl (DFBP) as template and 1H,1H,2H,2H-heptadecafluorodecyl acrylate/vinylanthracene as dual monomers. The structure, morphology and magnetic properties of MIA fabricated in the beneficial conditions were investigated by various characterized techniques. Under the optimal parameters, the prepared MIA presented satisfactory specific recognition performance. The recognition factor and adsorption capacity towards DFBP were as high as 2.7 and 15.9 mg/g, respectively. At the same time, the specific recognition behaviors of MIA/MSPE towards DFBP were surveyed by means of adsorption kinetics and adsorption isotherm. Combining with HPLC coupled with diode array detector (DAD), sensitive, reliable and anti-interference method for the monitoring of LCMs residuals in various environmental water and soil samples was established. The achieved enrichment factors were 132–248 and 96–204 in water and soil samples, respectively. The corresponding limits of detection were 0.0017–0.0051 µg/L and 0.087–0.28 µg/kg, respectively. Moreover, confirmatory experiments were adopted to inspect the accuracy of established MIA/MSPE-HPLC/DAD approach. To the best of our knowledge, this is the first time that using imprinted material to specific isolation and capture of LCMs which have been classified as emerging organic pollutants.