Composites of Sm doped TiO2 nanoparticles dispersed on carbon nanofibers (Sm-TiO2/CNFs) with different Sm contents were prepared by preoxidation, hydrolyzation and calcination of Sm-TiO2 precursor/PAN nanofibers. The characterizations of SEM, EDX, XPS and XRD showed that the CNFs surface was loaded by Sm-TiO2 nanoparticles with a uniform size of about 10nm, existing as anatase. It was concluded from XPS results that Ti element exist as Ti4+ and Sm doping increased the content of absorbed oxygen in composites. The effect of Sm doping on the photocatalytic activity of the Sm-TiO2/CNFs composite was investigated by the photocatalytic degradation of methyl orange aqueous solution under UV irradiation. It was found that Sm doping could improve the photocatalytic property of Sm-TiO2/CNFs effectively compared with the undoped specimen, and the photocatalytic activity of the Sm-TiO2/CNFs samples enhanced firstly and then reduced with Sm content increasing.