The core-shell nano-TiO2/Al2O3/NiFe2O4 microparticles of 5-8 microm were prepared by the heterogeneous precipitation followed by calcination treatment. The morphologies, structure, crystalline phase, and magnetic property were characterized by optical biomicroscopy (OBM), scanning electron microscopy (SEM), X-ray diffractometry (XRD) and vibrating sample magnetometer (VSM) respectively. The photocatalytic activity was evaluated by degrading methyl orange solution either under UV light and sunlight. The results indicate that the nano-TiO2 layer consists of needle-like nanoparticles and the intermediate layer of Al2O3 avoids the nano-TiO2 agglomeration, shedding and uneven loading. The nano-TiO2/Al2O3/NiFe2O4 composite particles show high magnetization of 31.5 emu/g and enhanced photocatalytic activity to completely degrade 50 mg/L methyl orange solution either under UV light and sun light. The enhanced activity of the composite is attributed to the unique structure, insulation effect of Al2O3 intermediate layer and the hybrid effect of anatase TiO2 and NiFe2O4. The obtained catalyst may be magnetically separable and useful for many practical applications due to the improved photocatalytic properties under sunlight.