In this research, a novel dummy molecularly imprinted polymer (DMIP) was prepared through a sol–gel process using bisphenol A as the dummy template and the synthesized 1-(triethoxysilyl) propyl-3-aminopropyl imidazole bromide (SilprImN) as the functional monomer. The prepared SilprImN-DMIP was characterized by FT-IR and verified with a satisfied identification and penetration performance to bisphenol A in static and kinetic adsorption tests. Furthermore, this novel DMIP was applied as a solid-phase extraction (SPE) material to develop a method for the simultaneous determination of nine organochlorine pesticides (OCPs) in environmental and food samples coupled to a multi dimensional gas chromatograph-mass spectrometer system. The SPE parameters, including sample acidity (pH), sample loading rate, the eluent and elution volume, were optimized in detail to achieve a good extraction efficiency. In water, rice and tea leaf samples spiked with nine OCPs, the OCPs were simultaneously determined with suitable recoveries from 65.65% to 129.61% and a good relative standard deviation (n = 3) of 0.91%–11.47%, indicating the satisfied accuracy and precision of the developed method.