The contamination of polycyclic aromatic hydrocarbons (PAHs) in edible oil is a health threat. Thus, trace analysis of PAHs is of high necessity. Based on the efficient adsorption of PAHs on Zn5 metal cluster, a Zn5 functionalized copolymer monolithic column was rationally designed for pipette tip micro-solid phase extraction (μ-SPE). The modified Zn5 improved the adsorption selectivity and capacity of the monolith for naphthalene, phenanthrene, fluoranthene and pyrene. Chemical doping and copolymerization stabilized the monolith with a long life. Under optimal extraction conditions, a μ-SPE-high performance liquid chromatography with ultraviolet detector method was established for the detection of 4 PAHs in edible oils. The method yielded detection ranges of 0.15–250 μg L−1 (R2 > 0.997), detection limits of 0.050–1.5 μg L−1, satisfactory recoveries (86.3–101.5 %), and high precisions (RSDs < 7.9 %). The results indicated that the Zn5 functionalized copolymer monolithic column was an ideal separation medium for the detection of PAHs residues in edible oils.