Two different phases of bismuth silicate nanofibers [Bi2SiO5 and Bi-4(SiO4)(3)] were synthesized using electrospinning technique. BS nanofibers were tested for the photocatalytic degradation of methyl orange and safranin O dyes. Different phases of BS affect the photodegradation efficiency of nanofibers. Impressive enhancement in photocatalytic efficiency and BET surface area of Bi-4(SiO4)(3) was observed over Bi2SiO5. A speedy reduction in dyes concentration was attributed to the rapid formation of oxygenated radicals by the capture of electrons and holes, generated in the BS nanofiber by UV irradiation. Therefore, the photocatalytic mechanism was elucidated using impedance spectroscopy at room temperature. The lower impedance value of Bi-4(SiO4)(3) nanofibers had improved high-efficiency charge transfer capability. The cycling efficiency (30 times) and recovery characteristics pointed out that Bi-4(SiO4)(3) nanofibers photocatalysts had high constancy, resilience, and regeneration ability.