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Background: Dental bleaching has become one of the most demanded aesthetic procedures as it is very simple and gives fast results that satisfy the patient’s wishes. However, unfortunately, it has the annoying side effect of tooth sensitivity. This clinical trial was designed to evaluate the efficacy of using a desensitizing agent, which was applied during in-office bleaching with 30% HP (hydrogen peroxide). Methods: 36 participants were divided into four groups (N = 9). According to the intended intervention as follows: Group I:—Application of Relief ®Amorphous Calcium Phosphate (ACP) before in-office bleaching; Group II—Application of Relief ®ACP before and after in-office bleaching; Group III—Application of Relief ®ACP after in-office bleaching; and Group IV: placebo was applied before and after in-office bleaching.  Then, three hydrogen peroxide bleaching applications for a total of 45 minutes were performed. The primary outcome variable was hypersensitivity, assessed with (VAS) scale immediately and 24h, 1 week and 1 month after the procedure; while the secondary outcome was teeth shade assessed using the VITAPAN ® classical shade guide. Results: Statistical analysis was done using Kolmogorov-Smirnov, Shapiro-Wilk tests, Kruskal-Wallis test and Dunn’s test. Immediately after bleaching, there was statistically significant distinction in the median pain score between the groups. After 1 day, the ACP gel before and after bleaching group showed the lowest median score, while, the control group confirmed the highest median score. After 2 days, no statistically sizable difference was observed between all groups. The group receiving ACP gel before and after showed the highest change in median of classical shade guide scores while, (ACP gel after) and control group; showed the lowest change. Conclusion: The application of the desensitizing agent prior to and after in–office bleaching was successful in lowering post-bleaching hypersensitivity. Trail Registration: Clinical trial.gov NCT02942082 21/10/2016

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