This paper reports the synthesis and characterizations of a new water-soluble poly(paraphenylene) (PPP) and its applications in preparing self-assembled multi-layer films. This new water-soluble conducting polymer was prepared through the sulfonation reaction of poly(pquarterphenylene- 2,2'-dicarboxylic acid). The incorporation of sulfonate groups has dramatically improved PPP's solubility in water at a wide pH range, whereas previous PPP is only slightly soluble in basic solutions. Dilute aqueous solutions of this polymer with acidic, neutral or basic pH emit brilliant blue light while irradiated with UV light. The sulfonated PPP emits from 350 nm to 455 nm with a maximum intensity at 380 nm. Self-assembled multilayers of this sulfonated PPP were constructed with a positively charged polymer poly(diallyl dimethyl ammonium chloride) and characterized with various surface analyses. Conductive (RuO2 and ITO), semiconductive (Si wafer), and non-conductive (SiO2) substrates were used in the preparation of self-assembled multilayers. Electrical, optical and structural properties of these novel self-assembled thin films will be discussed.