This study aims to synthesize hollow microspheres (HMS) from rape pollen via H3PO4 hydrothermal carbonization. The rape pollen hollow shell was used as the carrier and bovine serum albumin as a model protein. The properties of HMS were characterized by scanning electron microscope (SEM), solid-state nuclear magnetic resonance and elemental analysis. The SEM images clearly showed that the HMS had perfect spherical morphology and porous hollow surface. In the separated filtrate, a large number of sucroses were detected by high-performance liquid chromatography, suggesting that the hydrolysis of starch molecules occurred during the hydrothermal process. The formation of HMS was that the rape pollen inclusion was removed from rape pollen shell to preserve integral HMS by H3PO4 hydrothermal. The HMS possessed amphiphilic surfaces, which was suitable for protein adsorpion and pH-controlled release application.