We report a facile approach to fabrication and characterization of cationic titanium dioxide (TiO2 (+)) on poly (vinyl alcohol)/poly (acrylic acid) (PVA/PAA) composite electro-spun nanofibrous mat. The aim of this study is to develop a "functional electrospun nanofibrous mat" as a sustainable approach to superior photocatalytic degradation of organic colorants. For that, the PVA/PAA nanofibrous mat was prepared by electrospinning of PVA and PAA solution according to an aspect ratio of 1:1 and later water stability was induced by the thermal cross linking at an elevated temperature of 145 A degrees C for 30 minute. By means of electrostatic layer-by-layer (LbL) assembly, cationic titanium dioxide (TiO2 (+), 19 nm) was immobilized on the surface of the water stable nanofibrous mat. As functionalized composited nanofibrous mat was characterized by using scanning electron microscope (SEM), fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) analysis and thermogravimetric analysis (TGA). Superior competency of the functionalized nanofibrous mat towards photocatalytic degradation of organic dye (methyl blue) in aqueous solution was observed by using UV-visible spectrophotometer with quantitative measuring method. The result indicates a complete degradation of methyl blue within 40 mins and superior reusability upto 5 cycles application. The study signifies the prospect of using electrospun nanofibers to manipulate the catalytic activity, which could be a foundation for further rational design of various composite nanofibrous materials.