In this study, a highly sensitive and selective sample pretreatment procedure using molecularly imprinted silica nanoparticles was developed for the extraction and determination of quercetin in red wine samples coupled with high-performance liquid chromatography with ultraviolet detection. The imprinted silica nanoparticles were prepared in the presence of N-acryoyl-l-aspartic acid (functional monomer), quercetin (template), azobisisobutyronitrile (initiator) and methylene bisacrylamide (cross-linker) and methanol/water (porogen) via surface-initiated reversible addition-fragmentation chain transfer polymerization. Surface characterization was performed and several imprinting parameters were investigated, and the results indicated that adsorption of quercetin on the imprinted silica nanoparticles followed a pseudo-first-order adsorption isotherm with a maximum adsorption capacity at 26.4mg/g within 60min. The imprinted silica nanoparticles also showed satisfactory selectivity towards quercetin as compared with its structural analogues. Moreover, the imprinted nanoparticles preserved their recognition ability even after five adsorption-desorption cycles. Meanwhile, the nanoparticles were successfully applied to selective extraction of quercetin from red wine with a high recovery (99.7-100.4%). The limit of detection was calculated to be 0.058g/mL with a correlation coefficient 0.9996 in the range of 0.2-50g/mL. As a result, the developed selective extraction method using molecular imprinting technology simplifies the sample pretreatment procedure before determination of quercetin in real samples.