Using TiCl4 as the titanium source, urea as the precipitating agent, nano-TiO2/fly ash beads composite materials were prepared by hydrolysis-precipitation method. The materials were characterized by SEM and XRD methods. SEM observation shows that the surface of beads have been loaded a uniform TiO2 film. XRD results shows that TiO2 films have the main phases of anatase and rutile mixed crystal structure. The effect of surface activation process of fly ash beads on TiCl4 solution hydrolysis rate was studied. The influence of calcination temperature on the microstructure and properties of composite materials was also discussed. The photocatalytic properties of the prepared materials was measured by using UV-1800 uv-vis spectrophotometer. The results show that: The composite which calcined at 500°C has a grain size of 15nm, anatase phase content of 90%, shows the best photocatalytic effect. The degradation rate of methyl orange solution can reach 95% after 2 hours irradiation (300W, Mercury lamp). Repeated experiments show that the degradation rate of composite materials still reach 80% after being used for 5 times .