In the present study, the feasibility of the poly(divinyl-benzene vinylpyrrolidone) as solid-phase extraction (SPE) nanoscale adsorbent prior to LC-MS-MS method for the sensitive and selective determination of eight paralytic shellfish poisoning (PSP) (GTX1, GTX2, GTX3, GTX4, GTX5, dcGTX2, dcGTX3 and dcNEO-b) toxins in the shellfish was investigated. Various parameters affecting SPE efficiency including the eluent and its volume, and sample volume were studied. The application of the SPE can remove most of the ematrix interference compared with the conventional SPE procedure. By using slected reaction monitoring (SRM) mode in LC-MS-MS analysis, the acquired calibration curves were strictly linear (r2 > 0.996) for the eight targeted analyses. The feasibility of the proposed method was finally validated by quantifing the eight PSPs in the shellfish samples (scallop, Crassostrea gigas and Ruditapes philippinarum) with the satisfitory recoveries of more than 80% with RSDs less than 10%.