Abstract: Sol composition and ripening condition are two important parameters in silica fibers production through the conventional sol-gel process. In the current study, silica nanofibers were obtained successfully by electrospinning technique and sol-gel formation was performed during this process. Regarding previous reports, with the aim of increasing the selectivity, we used the molecular imprinted methodology to produce a selective medium via sol-gel electrospinning. In this process, sol-gel was formed during electrospinning and then the backbone polymer was removed by heating. To obtain a thin layer of silica nanofibers, the influencing parameters such as backbone polymer types, imprinting time and the components ratio were explored. The data obtained from Fourier transform infrared spectroscopy and thermogravimetric analysis revealed that the polyamide moiety is removed after heating and the scanning electron microscopy images indicated the geometry of the silica nanofibers before and after heating. The extraction efficiency of the electrospun silica nanofibers mat was compared with the same silica precursor sol-gel produced by bulk and electrochemical approaches. The data obtained from the online μ-solid phase extraction-liquid chromatography analysis demonstrated the superiority of electrospun silica nanofibers. After optimizing the whole procedure, the method was validated. The linearity of the analyte was in the range of 6-400 μg L-1 while the LOD value was 1.8 μg L-1 and the inter- and intra-day RSDs% were less than 9.6%. The method was conveniently applied to the spiked and un-spiked Zayanderood River and tap water samples with the relative recovery percentages up to 109%