As an efficient and easily available pesticide, imidacloprid (IM) has been widely used in agriculture to kill pests. However, threats to the ecological environment are becoming increasingly prominent, caused by abuse and pesticide residues. This paper reports a sensitive electrochemiluminescence (ECL) sensor based on upconverting nanoparticle functional zeolite imidazolate framework (UCNPs@ZIF-8) nanocomposites combined with molecularly imprinted polymers (MIPs) to successfully achieve the quantitative detection of IM. The composites exhibited a certain multi-faceted prismatic structure and the effective binding of UCNPs was demonstrated by characterization technology. In addition, a sensor with MIPs/UCNPs@ZIF-8/GCE as the working electrode exhibited outstanding ECL performance, including a strong and stable signal and excellent selectivity under optimal conditions. This sensor showed a good linear response to IM over a wide concentration range (0.1 ng L⁻¹–1 mg L⁻¹), with a limit of detection as low as 0.01 ng L⁻¹. More significantly, it was successfully applied to the determination of IM concentration levels in food, which provides broad application prospects for the construction of pesticide ECL sensors.