A facile magnetic solid phase extraction (MSPE) of aflatoxins (AFs) from liquid samples was developed using polydopamine-coated magnetic nanoparticles (PD-MNPs) as the adsorbent. PD-MNPs were prepared from amine-terminated MNPs and dopamine via an in situ oxidative self-polymerization approach. Under the selected MSPE conditions, extraction yields ranging from 59.3% for AF G2 to 89.0% for AF B1 were obtained with good repeatability. Coupled with HPLC-MS/MS quantification, the MSPE procedure serves not only for sample cleanup but also for AFs enrichment that is highly desired for trace analysis. The proposed MSPE-HPLC-MS/MS method had a linear calibration curve in the concentration range from 0.00600 to 3.00 ng/mL aflatoxin and limits of detection of 0.0012 ng/mL for AF B1, AF B2, and AF G1, and 0.0031 ng/mL for AF G2.