In recent years, pediatric dentistry has evolved considerably in terms of both the techniques and materials used. A clear, odorless liquid called silver diamine fluoride (SDF) is recommended for molars affected by hypoplasia and dentinal hypersensitivity. In adults and children who are at a high risk of developing caries, it is also helpful to prevent the progression of carious lesions. Teeth too compromised to be reconstructed that are not accompanied by discomfort or infection can be treated with SDF. The current review aims to provide an overview of the most recent research over the last 10 years on the potential of SDF, focusing on the clinical evidence of professionally applied fluoride therapy to prevent and arrest caries in children’s primary molars. Research was conducted according to the guidelines of the PRISMA statement. “silver diamine fluoride”, “primary molar”, and “primary molars” were the search terms utilized on the databases Scopus, Web of Science, and PubMed, with the Boolean operator “AND” and “OR”. Of these 195 studies, 13 primary studies were included in this review. The quality of the included papers was assessed using the reputable Cochrane risk of bias assessment for randomized trials. The studies reviewed consistently support the effectiveness of SDF in stopping the progression of existing caries in deciduous molars; on the contrary, there is insufficient evidence to draw conclusions about SDF being effective for the prevention of carious lesions in deciduous molars.