A bi-layer photoanode for dye-sensitized solar cell(DSSC) was fabricated, in which TiO_2 hollow spheres(THSs) were designed as a scattering layer and P25/multi-walled carbon nanotubes(MWNTs) as an under-layer. The THSs were synthesized by a sacrifice template method and showed good light scattering ability as an over-layer of the photoanode. MWNTs were mixed with P25 to form an under-layer of the photoanode to improve the electron transmission ability of the photoanode. The power conversion efficiency of this kind of DSSC with bi-layer was enhanced to 5.13 %,which is 14.25 % higher than that of pure P25 DSSC.Graphical Abstract A bi-layer composite photoanode based on P25/MWNTs-THSs with improved light scattering and electron transmission, which will provide a new insight into fabrication and structure design of highly efficient dyesensitized solar cells. A bi-layer photoanode for dye-sensitized solar cell (DSSC) was fabricated, in which TiO 2 hollow spheres were designed as a scattering layer and P25 / multi-walled carbon nanotubes (MWNTs) as an under-layer. The THSs were synthesized by a sacrifice template method and showed good light scattering ability as an over-layer of the photoanode. MWNTs were mixed with P25 to form an under-layer of the photoanode to improve the electron transmission ability of the photoanode. of this kind of DSSC with bi-layer was enhanced to 5.13%, which is 14.25% higher than that of pure P25 DSSC. Graphical Abstract A bi-layer composite photoanode based on P25 / MWNTs-THSs with improved light scattering and electron transmission, which will provide a new insight into fabrication and structure design of highly efficient dyesensitized solar cells.