In the tetrabutyl titanate solution via a sol-gel method, the nano-TiO2@polyfluorene composite particles were successfully prepared from the polyfluorene particles which were obtained by grinding fluorene with FeCl3 through the solid-state oxidative coupling reaction. The morphology and optical properties of the composite particles were characterized by scanning electronmicroscope, high resolution transmission electron microscopy, X-ray photo electron spectrometer, X-ray diffractometer, UV-visible diffuse reflectance spectroscopy, photoluminescence spectra and so on. The composite particles presented excellent photocatalytic activity on the degradation of triphenylmethane dyes, such as malachite green and rhodamine B under sunlight or under visible light. The photocatalytic reusability was investigated up to six successive cycles and the composite particles still retained their high activity of photodegradation ratio for malachite green. The mechanism of photocatalysis has been were discussed. The high surface area and effective photoinduced electrons and holes of TiO2@polyfluorene led to the enhanced photocatalytic activity. Consequently, the nano-TiO2@polyfluorene composite particles can be employed as an efficient photocatalyst to treat the organic pollutants.