SnOx with oxygen-rich vacancies and SnOx/N-GQDs (Nitrogen-doped graphene quantum dots) composites were prepared by high temperature annealing and hydrothermal method, respectively. The annealing process introduced a large number of oxygen vacancies and produced defect energy levels in the band gap. The existence of the defect level effectively reduced the band gap of SnOx, enlarged the optical absorption range, and improved the light utilization. The introduction of N-GQDs also improved the carrier density and electron transport rate, and extended the carrier lifetime (τ = 7.44 ms). I-T (Transient photocurrent response) analysis results showed that when the mass ratio of Sn/SnO2 was 1:4 and N-GQDs doping content was 1 wt%, the transient photocurrent response of SnOx/N-GQDs could reach 5.51 × 10−4 A/cm2, which was 25 times higher than that of pure SnO2, and the photocurrent response value maintained 80.1 % within 500 s. EIS (Electrochemical impedance) and M-S (Mott-Schottky) analyses indicated that the appropriate amount of oxygen vacancies and N-GQDs were beneficial to reducing the charge transport resistance, inhibiting the electron-hole pair recombination, and increasing the carrier density of SnOx. The results show that SnOx/N-GQDs composites present the improved photoelectric properties with the addition of oxygen vacancies and N-GQDs, which provides a new idea for promoting the properties of semiconductors.