In this paper, a straightforward method is presented to detect valproic acid after its microextraction. Molecularly imprinted polymer fiber was used in conjunction with chromatography-flame ionization to achieve this goal. A narrow bore silica capillary was adopted as a mold, via the copolymerization of meth acrylic acid–ethylene glycol dimethacrylate imprinted with VPA, to synthesize the fiber. Extraction temperature, extraction time, salt addition, pH, stirring rate, and desorption temperature—all of which are factors that can influence the extraction process—were measured, and adjusted accordingly. Linearity, precision, and detection limits, as analytical elements, were also evaluated under optimum conditions. Readings showed a linear range of 0.03–100 µg L−1 (r 2=0.998), and the limit of detection was measured as 0.01 µg L−1 . The established method was then applied in selective detection of valproic acid in tablet, syrup and human serum samples successfully.