All of the studies on solid-phase microextraction based on molecularly imprinted polymers up to now have been carried out on the synthesis of the polymer on the surface of the fiber which is brittle and the polymer coating strips during handling. The objective of this study was to develop a method for fabrication of a monolithic and robust solid-phase microextraction fiber on the basis of molecularly imprinted polymer for selective extraction of diacetylmorphine and its structural analogues followed by their GC or GC/MS analysis. A fiber was produced by copolymerization of methacrylic acid-ethylene glycol dimethacrylate imprinted with diacetylmorphine. The effective factors influencing the polymerization have been investigated and are detailed here. Also, the influences of pH, extraction time and temperature on the extraction efficiency of analytes were investigated. The prepared fiber was thermally stable up to 300 degrees C which has vital importance in SPME coupled with GC or GC/MS. The adsorption isotherm modeling was performed by fitting the data of studied compounds to bi-Langmuir isotherm model. The evaluated equilibrium constants for diacetylmorphine were 0.011 and 1824.72 microM(-1), and the number of binding sites was 170.37 and 4.64 nmolg(-1), respectively. This fiber was successfully used for extraction of template molecule from aqueous solution and further analysis with GC or GC/MS. The high extraction efficiency was obtained for diacetylmorphine, 6-monoacetylcodeine, and 6-monoacetylmorphine, yielding the detection limits of 300, 47, and 1 ngmL(-1), respectively.