Core-shell microspheres with Ni cores and two phases of TiO2 (anatase, rutile) shells have been successfully synthesized. The crystal structure, morphology and microwave absorption properties of the as-prepared composites were analyzed by X-ray diffraction, field-emission scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, and vector network analysis. The core-shell rutile TiO2-coated Ni exhibits better antioxidation ability than that of pure Ni due to the presence of the rutile TiO2 shell, which is confirmed by the thermal gravimetric analysis (TGA). In comparison with bare Ni, these two composites show better microwave absorption properties. The minimum reflection loss (RL) is -38.0 dB at 11.1 GHz with a thickness of only 1.8 mm for the Ni@TiO2 (rutile) composite. The enhanced absorption capability arises from the efficient complementarities between the magnetic loss and dielectric loss, multiple interfacial polarization, high thermal conductivity of rutile TiO2 and microwave attenuation constant. These results show that the thin high-efficiency rutile TiO2-coated Ni composite is a great potential microwave absorbing material for practical applications.