To evaluate the decomposition rate of active hydrogen peroxide (HP) and bleaching efficacy during in-office bleaching using high-concentration HP gels with different pHs. A randomized, parallel, double-blind controlled trial was conducted with 40 volunteers randomized into four groups (pH 5.4; pH 7.0; pH 7.7, and pH 8.0). During the first session in-office bleaching, approximately 0.01g of the gel was collected and titrated with potassium permanganate to obtain the concentration of active HP and pH values were measured using an electrode. Bleaching efficacy was assessed using a spectrophotometer [∆Eab, ∆E00, and WID], Vita Classical and Vita Bleachedguide scales [∆SGU]. The decomposition rate of HP concentration and pH values change were calculated using ANOVA one-way. The bleaching efficacy was assessed using two-way repeated measures ANOVA. Tukey's test was applied as a post-hoc test (p < 0.05). All gels experienced decreasing HP concentration over time. pH 5.4 gel showed greatest reduction after 50min (p < 0.001). pH 8.0 and 7.7 gels remained stable; pH 5.4 remained acidic, while pH 7.0 turned acidic (p < 0.001). No significant difference in bleaching degree was observed among gels. They all showed a similar and clinically important color change after two clinical sessions, remained stable 1-month post-treatment (p > 0.05). All bleaching gels kept at least 70% of their HP content after 50min, suggesting that there is a surplus of HP. They provided similar whitening efficacy 1-month after bleaching. It is possible that lower HP concentrations may be equally effective in achieving desired results while reducing the potential for side effects. RBR-35q7s3v.