The adsorption ability and photoactivity of a photocatalyst largely determine the mineralization efficiency of antibiotics. Herein, aiming to enhance the adsorption and mineralization of antibiotics, we constructed a hierarchical porous core-shell structure by filling amorphous TiO2 in the pores of Pt-doped mesoporous TiO2 crystals (MCs). The physical-chemical properties of the prepared samples were investigated by surface photovoltage spectroscopy, X-ray photoelectron spectroscope, etc. Adsorption and photocatalysis experiments were conducted with tetracycline hydrochloride as the model antibiotic. Pt nanoparticles doped at the interface of the rutile-amorphous homojunction remarkably enhanced the built-in electric field. The enhanced electric field increased the hole transfer to the catalyst surface, and the Pt doping treatment promoted the growth of amorphous TiO2 into the mesopores of the MCs. The optimization increased the surface area of the catalyst without increasing the thickness of the amorphous TiO2 shell, thereby reducing the charge migration distance from the core-shell interface to the catalyst surface. The adsorption amount and mineralization efficiency of tetracycline hydrochloride for the porous core-shell composite were 6.7 and 3.8 times of those for MCs, respectively.