Dendritic fiber-type silica (KCC-1) has attracted the attention of researchers because of its unique three-dimensional radial structure and high specific surface area. Its highly modified surface allows it to be used in catalysis, adsorption, biomedicine, and other fields. Nano-precious metals (NPs) have several excellent chemical properties, but their stability limits their applications. Dendritic fibrous silica (Ag NPs/KCC-1) loaded with silver nanoparticles was prepared via the microemulsion method using Ag NPs/KCC-1 as the carrier, methimazole as the template molecule, and a surface imprinting method to prepare sulfhydryl imidazole molecularly imprinted polymer. By characterizing the polymer, it is determined that the polymer has a regular morphology and large specific surface area. The obtained experimental results show that the polymer has a high adsorption capacity (10.35 mg g⁻¹) and good selectivity. It is used as a solid-phase extraction filler and, when combined with high-performance liquid chromatography, to detect methimazole in chicken tissue. The recovery rate reaches 87.5–94.4%.