This study developed experimental gels containing titanium tetrafluoride (TiF4) combined with commercial 35% hydrogen peroxide (HP), and evaluated bleaching efficacy and pH of the gels, and mineral content and morphology of enamel submitted to these treatments. In phase-1, different stock gels mixed with TiF4 were combined with HP. In phase-2, the selected gels were tested on enamel/dentin specimens (n=8): HP; HP and Natrosol+TiF4 (HPnT); HP and Natrosol+Chemygel+TiF4 (HPncT); HP and Aristoflex+TiF4 (HPaT). Bleaching was performed in four sessions (3x15min-application/session). Color (CIEL*a*b*) and whiteness index (WID) were measured after each session, whereas whiteness index differences (ΔWID), color alteration (CIELab-ΔE, CIEDE2000-ΔE00), enamel morphology and pH, at end of bleaching therapy. The change in Knoop microhardness (ΔKHN) was compared before and after bleaching. Data were analyzed by two-way repeated measures ANOVA and Bonferroni (CIEL*, a*, b*), one-way ANOVA and Tukey (ΔWID, ΔE, ΔE00), and LSD (ΔKHN) tests (α=5%). SEM and pH measurements were submitted to descriptive analysis. No differences were observed in lightness (L*) or WID among the groups (p > 0.05), but HP exhibited lower b* values (p<0.05), higher ΔWID than HPnT, and the highest ΔE among the groups (p < 0.05). No differences in ΔE00 were observed between HP and HPncT (p > 0.05), and HPncT showed higher ΔKHN than HP (p < 0.05). HP presented pH values closer to neutral (6.9), whereas experimental agents showed acidic pH values (2.3-3.9). No morphological changes were observed in HP or HPncT groups. HPncT was able to bleach the enamel and maintain enamel microhardness and surface integrity, even at low pH.