Fluorescent fibers were constructed from self-made bonded terbium polymer by electrospinning.The microstructure of the fibers was tuned and the luminescent properties were investigated by adjusting the properties of polymer solution such as solvent system and conductivity. The surface of the fibers is smooth, the diameter is the smallest, and the luminescent property is the best when V(DCE)∶V(DMF)=1∶2. When tetrabutyl ammonium chloride is added, the conductivity of the solution increases, the fiber diameter further reduces, but the luminescent performance deteriorates instead, because tetrabutyl ammonium chloride is weakly acidic. Fluorescence anti-counterfeiting paper was prepared by mixing pulp and fibers with V(DCE)∶V(DMF)=1∶2 solvent system. Fluorescent anti-counterfeiting fibers with both concealment and anti-counterfeiting properties were obtained. They can be applied to banknotes, bills, securities, and other important fields.