In this study, diisopropyl methylphosphonate (DIMP), tributyl phosphate (TBP), and dimethyl methylphosphonate (DMMP) were selected as organophosphorus chemical warfare agent (CWA) simulants. An effective surface acoustic wave (SAW) array sensor coated with three self-assembled imprinted supramolecular films and two polymer coatings was prepared to detect CWA simulants at low concentrations. As a supramolecular film, 25-(thioalkyl-alkoxy)-p-tertbutylcalix[4]arene was synthesized via a two-step nucleophilic substitution reaction in the NaH–THF phase with p-tertbutylcalix[4]arene and dibromodecane. Then, 25-(thioalkyl-alkoxy)-p-tertbutylcalix[4]arene, 1,7,13,20-four-(thioalkyl-alkoxy)-resorcin[4]arene, and mono[6-deoxy-6-[(mercaptodecamethylene)thio]]-β-CD were coated on SAW gold delay lines using a self-assembly method to detect DIMP, DMMP, and TBP, respectively, proving the imprinting effect. The response frequency shifted to DIMP and exhibited a linear relationship in the concentration range of 0.05–0.60 mg m⁻³. The sensitivity of the SAW sensor was also examined at different temperatures, and the possible mechanism of interactions between the supramolecular coatings and DIMP was discussed. To further prove the effect of supramolecular films, a SAW array sensor was prepared with supramolecular 25-(thioalkyl-alkoxy)-p-tertbutylcalix[4]arene, mono[6-deoxy-6-[(mercaptodecamethylene)thio]]-β-CD, 1,7,13,20-four-(thioalkyl-alkoxy)-resorcin[4]arene, and polymers fluoroalcoholpolysiloxane (SXFA) and poly(epichlorohydrin) (PECH) for detecting DIMP, DMMP, TBP, and 2-chloroethyl ethyl sulfide. The results indicated that the fabricated SAW array sensor was highly sensitive to CWAs and may be used to distinguish CWAs and their related compounds. In the three supramolecular self-assembled imprinted coatings, the aging experiments proved that the response of the SAW array sensor may decrease to approximately 23%, 11%, and 17% after 18 months of storage.