SnO2 is a wide-band gap N-type semiconductor material with a higher electron transfer rate than TiO2. Therefore, SnO2 has broad application prospects in the photoanode composite materials of dye-sensitized solar cells (DSSC). In this study, SnO2–TiO2 composite nanofibers with different molar ratios (5%, 10%, 15%, and 20%) were prepared by double-needle electrospinning technology, and the nanofibers were characterized after adjusting the solution composition. Different molar ratios of TiO2 and SnO2–TiO2 composite nanofiber photoanodes were fabricated by spin-coating, and the adsorption behavior of dyes on the photoanodes was investigated. Moreover, the electrochemical impedance of the photoanodes and DSSC and their photoelectric performance were also tested. The experimental results showed that SnO2–TiO2 composite nanofibers with a molar ratio of 10% exhibited excellent properties, including a peak specific surface area of 93.01 m2/g, strong dye adsorption capacity, small interfacial resistance, and fast electron transfer rate. These outstanding properties significantly promoted the generation of photoelectrons and improved the photoelectric conversion efficiency of DSSC. Compared with single-component TiO2, the photoelectric conversion efficiency of SnO2–TiO2 nanofiber photoanode composite material improved by 85.65%.