Nano-sized molecularly imprinted polymer (nMIP) was synthesized through precipitation polymerization method and used it as solid phase extraction (SPE) sorbent for the selective and simultaneous extraction of hydroxylated metabolites of polycyclic aromatic hydrocarbons (PAHs) from urine followed by ultra-high performance liquid chromatography (UHPLC) analysis coupled with the fluorescent detector (FLD). Multi-template imprinting approach was used in the synthesis of nMIP by taking 1-naphthol, 9-phenanthrol and 9-hydroxyfluorene as templates, methacrylic acid (MAA) as a monomer, ethyleneglycoldimethacrylate (EGDMA) as a crosslinker and AIBN as an initiator. The synthesized nMIP exhibit the highest degree of binding affinity in comparison to non-imprinted polymer (NIP), and its binding affinity found to be in the range of 50-90% for all five metabolites tested. Method exhibits good linearity over a range of concentrations of metabolites with a R(2) value ranges from 0.9789 to 0.9921. Limit of detection (LOD) and limit of quantitation (LOQ) in urine samples were found to be in the range of 0.33-2.6 and 0.99-8ngmL(-1), respectively. Precision study shows that intra and inter-day precision was found to be less than 10%. The application of nMIP as SPE sorbent offers an effective and selective affinity towards the PAH metabolite's and found to be an alternative to the conventional sorbent for PAH metabolite's extraction from the biological samples. The developed nMIP offers wide advantages like simultaneous determination of PAH metabolites with improved sensitivity and found to be cost-effective for the routine analysis.