A series of waterborne polyurethane prepolymer were prepared by sophorone diisocyanate (IPDI) and polycaprolactone glycol (PCL1000) as the main raw materials, dimethylol propionic acid (DMPA) as hydrophilic chain extender. The waterborne polyurethane (SWPU) with fluorescence was obtained by 4,4'-Diaminodiphenylethylene-2,2'-disulfonic acid (DSD acid) as chain extender. Structure and properties of polymer were characterized by FT-IR, DLS, XRD, UV-Vis, Fluorescence spectra, Tensile testing and TGA&DTG. FTIR, DLS analysis showed that DSD acid had been introduced into the molecular chain of SWPU, with the increase of the mass fraction of DSD acid, the particle size of emulsion decreases firstly and then increases. When w (DSD acid) =2%, the particle size of SWPU emulsion was 72.80 nm. The results of XRD, UV-vis and fluorescence spectra showed that SWPU had obvious crystallinity, SWPU had certain ultraviolet absorption and red shift, SWPU emit strong blue fluorescence and concentration quenching. Compared with the WPU, the thermal stability of SWPU latex film the tensile strength and the maximum decomposition temperature had improved obviously. When w (DSD acid) =3%, the maximum tensile strength was 48.43 Mpa and the elongation at break was 366.42%, the maximum decomposition temperature from 301.48 ℃ to 328.05 ℃.