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To assess the effect of bleaching with gel of pregabalin associated with 35% hydrogen peroxide on the mechanical and chemical properties and ultramorphology of dental enamel. Thirty-six (36) specimens of bovine dental incisors were obtained and divided into three groups (n = 12), namely: CG = bleaching with 35% hydrogen peroxide; KFG = bleaching with 5% potassium nitrate and 2% sodium fluoride gel + 35% hydrogen peroxide; and PGG = bleaching with experimental gel of pregabalin + 35% hydrogen peroxide. The specimens were assessed with respect to Knoop microhardness, surface roughness, and colour change, before and after bleaching. They were also assessed using scanning electron microscopy and energy-dispersive spectroscopy after treatments. All groups exhibited an increase in surface roughness and a reduction in Knoop microhardness after the protocols. There was colour change in all groups, with no difference between them. In addition, there were changes in enamel morphology and non-significant loss of calcium and phosphorus. The experimental gel of pregabalin did not influence the action of 35% hydrogen peroxide, yielding results similar to those of the other groups assessed in all the parameters. Therefore, the gel of pregabalin can be an alternative for topical application on the surfaces of the teeth in association with bleaching treatments., Competing Interests: Declarations. Conflict of interest: The authors declare no competing interests. Ethics approval: This study does not involve humans or animals. The local ethic committee in research has confirmed that no ethical approval is required., (© 2024. The Author(s), under exclusive licence to The Society of The Nippon Dental University.)