A simple one-pot approach based on molecularly imprinted polymer shells dispersed on the surface of silica for simultaneous determination of rhodamine B and dibenzyl phthalate (DBzP) has been developed. Highly dense molecularly imprinted polymer shells were formed in the mixture of acetonitrile and toluene by the copolymerization of methacrylic acid and ethylene glycol dimethacrylate, as well as two templates, rhodamine B and dibenzyl phthalate, directed by the vinyl end groups functional monolayer at surface silica microspheres after 3-methacryloxypropyl trimethoxysilane modification. The obtained imprinted polymer shells showed large average pore diameter (102.5 nm) and about 100 nm shell thickness. The imprinted particles also showed high imprinting factor (_RhB = 3.52 and _DBzP = 3.94), rapid binding kinetics, and excellent selective affinity capacity for rhodamine B and dibenzyl phthalate containing another three competitors in mixed solution. Moreover, the imprinted particles coupled with ultra high performance liquid chromatography was successfully applied to simultaneous analysis of rhodamine B and dibenzyl phthalate in two spiked beverage samples with average recoveries in the range of 88.0−93.0% for rhodamine B and 84.0–92.0% for dibenzyl phthalate with the relative standard deviation lower than 5.1%.