Bi deposited Yb3+, Er3+ codped TiO2 nanofiber photocatalysts were synthesized from Yb3+ and Er3+ Co - doped TiO2 substrate by combining electrospinning technique and hydrothermal method. Using triethanolamine as a sacrificial agent, we studied the ultraviolet, visible, near infrared and full spectrum photocatalytic hydrogen production over Bi/Yb3+, Er3+:TiO2. The results showed that the full-spectrum illumination for 5 h resulted in a hydrogen production rate of 1 650.3 mu mol.g(-l).h(-1). As an emerging non-noble metal, Bi displays unique plasma photocatalytic or assisted photocatalytic properties. The advantages of Bi metal can be further combined with a rich energy level structure of rare earth elements and unique up-conversion luminescence properties. The double synergistic modification of TiO2 can effectively improve the photocatalytic activity of TiO2 nanofibers.