Dentin hypersensitivity (DH) pain is a persistent clinical problem, which is a common condition known to affect patients’ quality of life (QoL), but no treatment has ever been agreed upon. Calcium phosphates, available in different forms, have properties that allow sealing the dentinal tubules, which may relieve dentin hypersensitivity. The aim of this systematic review is to evaluate the ability of different formulations of calcium phosphate to reduce dentin hypersensitivity pain level in clinical studies. The inclusion criterion was as follows: clinical randomized controlled studies using calcium phosphates in treating dentin hypersensitivity. In December 2022, three electronic databases (Pubmed, Cochrane and Embase) were searched. The search strategy was performed according to Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines. The bias assessment risks results were carried out using the Cochrane Collaboration tool. A total of 20 articles were included and analyzed in this systematic review. The results show that calcium phosphates have properties that reduce DH-associated pain. Data compilation showed a statistically significant difference in DH pain level between T0 and 4 weeks. This VAS level reduction is estimated at about −2.5 compared to the initial level. The biomimetic and non-toxic characteristics of these materials make them a major asset in treating dentin hypersensitivity.