Titanium dioxide (TiO2) is one of the excellent photocatalysts used for degradation of environmetal pollutants. In this work, 2.5, 5.0 and 7.5 wt.% of silver (Ag)-loaded TiO2 nanofibers of mean size 52–134 nm were synthesized by electrospinning method. These electrospun nanofibers were calcined at 500 °C to enable the transformation of Rutile (R) phase to Anatase (A), elimination of reaction moieties from the TiO2 matrix and subsequently formation of Ag clusters. The effect of Ag loading on the morphology, crystal structure, phase transformation, and band gap of these electrospun nanofibers have been characterized by scannining electron microscopy (SEM), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), raman spectroscopy and UV-visible spectroscopy. These nanofibers exhibited a red-shift in the absorbance edge and a significant enhancement of light absorption in the wavelength range of 250–550 nm. These electrospun nanofibers were investigated for photodecomposition of methylene blue (MB), and photocatalytic decolorization rates were determined by pseudo-first-order equation. The rate constants for the pure and those of 2.5, 5.0, and 7.5 wt% Agloaded TiO2 nanofibers were computed to be 0.1439 min-1, 0.1608 min-1, 0.1876 min-1, and 0.2251 min-1 respectively.