A novel UV-light-active MCC/S-VO2 photocatalyst was successfully synthesized by a simple and reliable hydrothermal route. XRD, FT-IR, Raman analysis, XPS, FE-SEM, EDX, TEM, DRS, and thermal analysis techniques were utilized for the characterization of the as-prepared photocatalysts. The photocatalytic activities of the V2O5, doped S-VO2, and MCC/S-VO2 nanostructures were investigated by monitoring the fading out of the methylene blue (MB) concentration under UV-light irradiation. The results revealed that the photocatalytic degradation of MB via MCC/S-VO2 was superior compared with that exhibited by pure V2O5 and doped S-VO2. It was found that 72.3% of MB (100 mL; 20 mg·L−1) was degraded after 6 h in contact with MCC/S-VO2. Interestingly, the photodegradation of MB dye was enhanced dramatically by adding H2O2, while 92.5% of MB was degraded within 55 min. The kinetic studies revealed that the MB degradation followed the pseudo-first-order model with a rate constant (kobs) of 3.9 × 10−2 min−1. The effect of several active species scavengers on the photocatalytic degradation process was investigated. The data exhibited that hydroxyl radicals and positive holes were the key active species during the degradation process. The stability and reusability of the as-prepared nanostructures were examined, and the results displayed its applicability for the removal of MB dye from aqueous media.