Using diethylenetriamine and 2,4-tolylene diisocyanate as basic reactive materials, hollow polyurea microspheres were synthesized via interfacial polycondensation in inverse miniemulsion at room temperature. The effects of emulsifier, continuous phase, dispersed phase and stabilizer on the stability of inverse miniemulsion and morphology of the hollow microspheres were investigated. The morphology and structure were characterized by transmission electron microscopy and fourier transform infrared spectroscopy. Research shows that the polyurea hollow microspheres are synthesized with Span80 as the surfactant, formamide as the dispersed phase, cyclohexane as continuous phase and AgNO3 as the stabilizer. The size and wall thickness of hollow microspheres are about 100 nm and 17 nm respectively. The drug loading and release properties of nano hollow microspheres were investigated with Rhodamine B as a model drug. The results show that the maximum adsorptive capacity reaches 101 mg Rhodamine B per 1.00 g of the hollow microspheres (101 mg/g) and its release time reaches 14 h or more.