Multifunctional ionic liquid monomer (1) was synthesized from 1‐vinylimidazole and 2‐acrylamido‐2‐methylpropane sulphonic acid (AMPS) and alternately copolymerized from 3‐mercaptopropyltrimethoxysilane grafted silica core (2) to obtain hybrid core‐shell particles Sil‐PIL.1. Elemental analysis and 13C CP/MAS results confirmed that the ionic monomers retained the alternation after grafting on silica surface, which make it a promising candidate as sorbent for trapping analytes from aqueous and other samples for solventless microextraction processes. The material demonstrated excellent extraction efficiency for low molecular weight polar compounds and the peak areas for derivatized aldehydes can be increased up to 200 times in comparison with a commercial polydimethylsiloxane (PDMS) sorbent.