Abstract: In this work, we present a fast, simple and selective method for the extraction/preconcentration and determination of five opium alkaloids. This method is based on the combination of dispersive solid phase extraction with magnetic molecularly imprinted polymers (MMIP) and determination via high performance liquid chromatography. The surface modified Fe3O4 nanoparticles were synthesised in-situ, from a co-precipitation method by addition of a mixture of the methacrylic acid and ammonia to a mixture of Fe2+/Fe3+ under nitrogen atmosphere. MMIP was prepared from surface modified nanoparticles in the presence of ethylene glycol dimethyl acrylate as cross-linker and azobisisobutyronitrile as initiator and template molecule under reflux in acetonitrile. MMIPs for five natural occurring opium alkaloids, including morphine (MO), codeine (CO), thebaine (TE), noscapine (NO) and papaverine (PA) were prepared in the same manner. Structural characterisation and elucidation of both synthesised nanoprticles were performed by Fourier transform-infrared spectroscopy, scanning electron microscopy. X-ray diffraction and vibrating sample magnetometry. A precise chromatographic method was developed and coupled with extraction with MMIP nanoparticles for simultaneous preconcentration and determination of above-mentioned alkaloids in underground water samples. The limit of detection obtained 0.007, 0.007, 0.004, 0.003, 0.003 mg L-1 for MO, CO, TE, NO and PA, respectively and recoveries were about 97-102%. Linear dynamic range and relative standard deviation were 0.03-100 mg L-1 and less than 1.5% for each analyte