Polyaniline-modified CoFe2O4–TiO2-nanocomposites (PCT) with hierarchical flower-like nanoarchitectures were successfully synthesized by a facile procedure. The PCT particles with diameters about 420–600 nm possess both nano- and micro-scale structures, and exhibit excellent light absorption properties both under UV and visible light irradiation. Meanwhile, it shows a dramatic enhancement of photocatalytic activity compared with corresponding PANI–CoFe2O4 and CoFe2O4–TiO2 samples. The excellent photoactivity of PCT can be attributed to the synergistic effect of PANI, TiO2, and CoFe2O4 in the ternary system, which leads to a rapid charge separation and slow charge recombination thereby resulting in a higher photocatalytic activity. In addition, the ferromagnetic properties of CoFe2O4 are maintained in the PCT composite to some extent, which can facilitate their separation from the liquid phase via application of an external magnetic field. Therefore, PCT nanocomposites are promising candidates for the effective photocatalytic treatment of wastewater.