Molecularly imprinted polymers (MIPs) of dopamine (DA) were constructed on the surface of graphene oxide (GO), and attached inside the pores of hollow fibers (HFs) for the solid-phase microextraction (SPME) of DA. Scanning electron microscopy, thermogravimetric analysis and Raman spectroscopy indicated that GO–MIP composites were successfully synthesized and modified in the pores of HFs via ultrasonication. Compared with common HFs and HFs modified with non-imprinted polymers (GO–NIP/HF) using the same SPME procedures, the GO–MIP/HF composites showed the best efficiency for the extraction of DA. The selectivity of GO–MIP/HF was investigated based on the selectivity factor (F) using epinephrine and norepinephrine as the structural analogues of DA. The linear range of dopamine was 1.05 × 10−3 to 5.27 × 10−3 μmol mL−1, using this process with a detection limit of 2.64 × 10−4 μmol mL−1. The extraction procedure based on GO–MIP/HF was successfully used for the determination of DA in human serum and its hydrochloride injection, showing average recoveries of 83–96%. GO–MIP/HF was a good carrier for the selective adsorption of DA, and showed promise for the preconcentration of DA in real samples.
