In this study, a simple preparation approach was developed for modified bisphenol A (BPA) molecularly imprinted polymer sorbent used in the hollow fiber solid phase microextraction (MIP-HF-SPME) of chlorogenic acid (CGA). The pre-polymer solution containing the template was introduced into the polypropylene hollow fiber segment for in situ polymerization. MIP-HF-SPME conditions based on the modified MIP-sorbent were optimized. Finally, the tool was used for selective extraction of chlorogenic acid in Echinacea purpurea, a medicinal plant. Main parameters affecting synthesis of organic–inorganic hybrid MIP and microextraction procedure were investigated and optimized. The measurements were done under the optimal conditions. The limit of detection has been gained 0.08 ng/mL. The linear range and relative standard deviation (RSD %) are 0.2–1000 ng/mL and 0.38 (n = 3) respectively. The average relative recoveries of spiked analyte in the four concentration levels were between 84.8 and 97.2%.