TiO2/WO3 nanofibers were prepared in a one-step process by electrospinning. Titanium(IV) bis(ammonium lactato)dihydroxide (TiBALDH) and ammonium metatungstate (AMT) were used as water-soluble Ti and W precursors, respectively. Polyvinylpyrrolidone (PVP) and varying ratios of TiBALDH and AMT were dissolved in a mixture of H2O, EtOH and CH3COOH. The as-spun fibers were then heated in air at 1 °C min−1 until 600 °C to form TiO2/WO3 composite nanofibers. Fiber characterization was done using TG/DTA, SEM–EDX, FTIR, XRD, and Raman. The annealed composite nanofibers had a diameter range of 130–1940 nm, and the results showed a growth in the fiber diameter with an increasing amount of WO3. The photocatalytic property of the fibers was also checked for methyl orange bleaching in visible and UV light. In visible light, the photocatalytic activity increased with an increase in the ratio of AMT, while 50% TiBALDH composite fibers showed the highest activity among the as-prepared fibers in UV light.