BACKGROUND Binary functional monomers, allyl‐β‐cyclodextrin (allyl‐β‐CD) and methacrylic acid (MAA) or allyl‐β‐CD and acrylonitrile (AN), were exploited in a fabrication of molecularly imprinted polymers (MIPs) for selective recognition and large enrichment of pirimicarb from aqueous media. RESULTS Special attention was paid to the computational simulation of the imprinting molecular and functional monomers. The morphological characteristics of MIPs made of allyl‐β‐CD and MAA (M‐MAA) were characterised by scanning electron microscopy. The effect of binding capacity of MAA‐linked allyl‐β‐CD MIPs (M‐MAA) demonstrated higher efficiency than that of AN‐linked allyl‐β‐CD MIPs (M‐AN) when tested in binding specificity. Finally, M‐MAA was chosen to run through molecularly imprinted solid‐phase extraction (MISPE) to analyse the spiked fresh leafy vegetables of pirimicarb. CONCLUSION The present proposed technique is a promising tool for the preparation of the receptors which could recognise pirimicarb pesticide in aqueous media. © 2017 Society of Chemical Industry