Electro-spun fabricated TiO2 nanofibers were prepared by simple electro-spinning method, in subsequent step silver (Ag) was deposited using precipitation method and obtained Ag-TiO2 composite nanofibers. The properties and morphology of these prepared composite nanofibers were characterized by XRD, SEM, EDX, and TGA. The prepared electro-spun composite nanofibers were applied as catalyst for the photodegradation of Congo-red under immited solar light in aqueous solution. Result reveals that, Ag loaded TiO2 composite nanofibers were effectively increased photodegradation of Congo red compared with pure TiO2 nanofibers in analogous condition. As a result, 92.0% decomposition of Congo red was obtained by using 5 wt% of Ag loaded TiO2 composite nanofibers at room temperature in short reaction time using 300 W of solar light. In addition, photodegradation of Congo red was also studied under different experimental conditions such as amount of Ag loaded in TiO2 nanofibers and contact time. Moreover, we also studied sintering effect on TiO2 nanofibers and their consequent effect on photodegradation reaction. After completion of reaction, the nanofibers can be easily separated by filtration process and reused several times without significant loss of activity. Overall study reveals that, Ag-TiO2 composite nanofibers were strongly enhanced the surface activity for the photo catalytic degradation of Congo red under ambient condition.