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Na2Ti6O13/TiO2 composite particles were synthesized through the hydrolyzation of tetrabutyl titanate in a reverse microemulsion and characterized by thermogravimetry and differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), and scanning electron microscope (SEM). The photocatalytic property of Na2Ti6O13/TiO2 was evaluated by degradation of 2,4-dichlorophenol(2,4-DCP) under 40 W ultraviolet lamp (λ=365 nm) irradiation and compared with commercial P25-TiO2 in the same condition. The results showed that the synthesized nanobelts Na2Ti6O13/TiO2 heterostructures had typical width from 80 to 100 nm, with thickness less than 40 nm and length up to 5 μm. Such Na2Ti6O13/TiO2 nanosized particles exhibited better photocatalytic activity than that of P25-TiO2, and the degradation rate of 2,4-DCP with initial concentration of 0.02 g/L reached 99.4% at the end of 50 min.