Rare earth fluoride EuF3 and TbF3 were coated on the multi-walled carbon nanotubes (MWNTs) via the intermediate of noncovalent hydrophobic interactions of the MWNTs surface with sodium dodecyl sulfate (SDS).They were characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM). The nanoparticle sizes of metal fluorides and sulfides on MWNTs are less than 20 nm. The photo physical properties of the composites were investigated, which indicated the composites exhibited the optical transitions within the 4f shell of the rare earth ions.