A series of multifunctional water-soluble polymeric fluorescent whitening agents (PFWAs, 5a-f) based on 4,4′-diamino-stilbene-2,2′-disulfonic acid (DSD acid)-triazine structure were successfully synthesized using a nucleophilic substitution reaction with cyanuric chloride, DSD acid, amino compounds, polyethylene glycol (PEG), and/or polyvinyl alcohol (PVA) as raw materials. The structure of the PFWAs was characterized by FT-IR, and the substitution degree was calculated from the results of an elemental analysis. The optical properties of the PFWAs were measured by the UV-vis spectra and fluorescence spectra when the PFWAs were applied to paper fiber to serve the roles of light stabilizer, fluorescent whitener, and surface-sizing agent. Then the performance of the PFWAs on paper was evaluated by measuring the surface strength and smoothness of paper, brightness degree of paper, and the yellowness value (value of PC) of paper. The results indicated that the PFWAs had better light stability in water solution than that of a conventional fluorescent whitening agent (FWA) as a light stabilizer. According to the surface-sizing experiment and UV aging experiment, it was concluded that not only could the PFWAs enhance the surface strength and smoothness of paper, but also have a better effect on anti-UV aging than that of FWA as a light stabilizer and fluorescent whitener agent.