Abstract A novel core-shell composite of gold nanoparticles (AuNPs) and SiO2 molecularly imprinted polymers ([email protected]) was synthesized through sol–gel technique and applied as a molecular recognition element to construct an electrochemical sensor for determination of dopamine (DA). Compared with previous imprinting recognition, the main advantages of this strategy lie in the introduction and combination of AuNPs and biocompatible porous sol–gel material (SiO2). The template molecules (DA) were firstly adsorbed at the AuNPs surface due to their excellent affinity, and subsequently they were further assembled onto the polymer membrane through hydrogen bonds and π–π interactions formed between template molecules and silane monomers. Cyclic voltammetry (CV) was carried out to extract DA molecules from the imprinted membrane, and as a result, DA could be rapidly and effectively removed. The [email protected] was characterized by ultraviolet visible (UV–vis) absorbance spectroscopy, transmission electron microscope (TEM) and Fourier transform infrared spectrometer (FT-IR). The prepared [email protected] sensor exhibited not only high selectivity toward DA in comparison to other interferents, but also a wide linear range over DA concentration from 4.8×10−8 to 5.0×10−5M with a detection limit of 2.0×10−8M (S/N=3). Moreover, the new electrochemical sensor was successfully applied to the DA detection in dopamine hydrochloride injection and human urine sample, which proved that it was a versatile sensing tool for the selective detection of DA in real samples.