This study describes the design, synthesis, and application of polymeric ionic liquid sorbent coatings featuring nickel metal centers for the determination of volatile and semi‐volatile amines from water samples using headspace solid‐phase microextraction. The examined polymeric ionic liquid sorbent coatings were composed of two ionic liquid monomers (tetra(3‐vinylimidazolium)nickel bis[(trifluoromethyl)sulfonyl]imide [Ni2+(VIM)4] 2[NTf2–] and 1‐vinyl‐3‐hexylimidazolium [HVIM+][NTf2–]), and an ionic liquid crosslinker (1,12‐di(3‐vinylimidazolium)dodecane [(VIM)2C122+] 2[NTf2–]). With these ionic liquid monomers and crosslinkers, three different types of coatings were prepared: PIL 1 based on the neat [Ni2+(VIM)4] 2[NTf2–] monomer; PIL 2 consisting of the [Ni2+(VIM)4] 2[NTf2–] monomer with addition of crosslinker, and PIL 3 comprised of the [HVIM+][NTf2–] monomer and crosslinker. Analytical performance of the prepared sorbent coatings using headspace solid‐phase microextraction GC‐MS was compared with the polydimethylsiloxane and polyacrylate commercial coatings. The PIL 2 sorbent coating yielded the highest enrichment factors ranging from 5500 to over 160000 for the target analytes. The developed headspace solid‐phase microextraction GC‐MS method was applied for the analysis of real samples (the concentration of amines was 200 μg L–1), producing relative recovery values in the range of 90.9‐120.0 % (PIL 1) and 83.0‐122.7 % (PIL 2) from tap water, and 84.8‐112.4 % (PIL 1) and 79.2‐119.3 % (PIL 2) from lake water.