Experimental results of photocatalysis under high dissolved oxygen (DO) concentration conditions are reported. Methylene blue was used as the organic pollutant to be degraded by a novel microwave/UV/DO/TiO2 photocatalyst hybrid system. The degradation rate increased with TiO2 nanoparticle dosages and DO concentration. However, inhibition of photocatalysis due to bubbles produced by DO generator was also observed. When the DO generator was used to increase the DO concentration in the pollutant solution treated by the microwave-assisted UV-TiO2 photocatalysis, the decomposition rate constant was highest among all the experimental conditions tested in this study. This result demonstrated that high concentration of DO can enhance the photocatalytic reaction rate by causing a synergistic effect of constituent techniques.