Although the traditional SERS metal substrates have high sensitivity, their unrepeatable and ecological environment unfriendly performance greatly limits their applications. Therefore, it is necessary to explore multi-functional SERS substrates with recyclability, photocatalytic degradation, and ultra-sensitive detection ability. Herein, the Nb2O5 ultra-thin nanosheets were successfully synthesized by a simple hydrothermal method. Based on the coupled resonance effect, the SERS sensitivity of Nb2O5 substrates was optimized by the Mo doping process. The SERS enhanced factor EF of Mo-Nb2O5-MV at 1617 cm−1 with the irradiation laser of 532 nm is determined to 2.09 × 107 and the corresponding substrate possesses a low detection limit of 10−8 M, which can parallel the noble metal SERS substrates without “hot spots”. The enhanced Raman signals of MV on Mo-Nb2O5 substrates are mainly originated from photo-induced charge transfer resonance between molecules and semiconductor clusters. It is noticeable that Mo-Nb2O5 ultra-thin nanosheets substrates not only exhibit excellent SERS sensitivity and uniformity but also have recyclability, stability and rapidly photocatalytic degradation ability of dye molecules in visible-light, which expend the application of semiconductor SERS substrates in the detection and treatment of pollutants.