This paper presents a study of the synthesis of a polymer monolith column and its application to the analysis of PAHs in smoked meat products. A poly(butyl methacrylate-co-ethylene glycol dimethacrylate) monolith capillary has been successfully prepared with in situ polymerization method. The polymer monolith microextraction combined with HPLC determinations is employed for the analysis of naphthalene, biphenyl, phenanthrene, and anthracene. Various parameters affecting the extraction efficiency have been investigated and optimized. Under the optimum experimental conditions, the method provides an acceptable linearity (2–10,000 μg/L), low limits of detection (1.4–2.0 μg/L), and good precision (intraday relative standard deviations < 4.1%, interday relative standard deviations < 5.7%). When applied to the determination of the four PAHs in smoked meat samples, recoveries are obtained in the range of 86.6–101.5%.