Zearalenone (ZEN) is one of the most prevalent mycotoxins worldwide, yet the extraction and determination of ZEN remain challenging due to difficulties in its purification from the food matrix. In this study, rice husk-derived mesoporous silica (MS) particles were surface-modified with molecularly imprinted polymers (MS@MIPs). The MS@MIPs featured a dense and homogeneous texture with an average particle size of ca. 550 nm, which had an imprinting factor of 5.17 for ZEN. When applied in solid phase extraction (SPE) by packing MS@MIPs and MS (80:20) in a polypropylene column (MIP-SPE), the recovery rate for ZEN deliberately spiked in maize extract reached 94.34%. This was dedicated to facile detection of ZEN by high-performance liquid chromatography with a fluorescence detector (MIP-SPE-HPLC-FLD) showing a linear response to ZEN at 5.0–100 μg/kg with a good R2 of 0.991 and excellent limit of detection and limit of quantification of 1.5 μg/kg and 5.0 μg/kg, respectively. Furthermore, MIP-SPE had good stability with high recovery (≥87.7%) after 5 repeated operations. The results indicated that the MIP-SPE-HPLC-FLD was a facile method for the accurate determination of ZEN in maize.