The development of biomaterials for direct pulp capping has significantly transformed modern vital pulp therapy. For decades, calcium hydroxide was considered the gold standard, but its limitations—such as lack of sealing ability and tendency for resorption—have prompted the search for improved solutions. The introduction of calcium silicate cements and new-generation bioceramics has led to better biological and clinical outcomes. This review aims to discuss the latest advances in biomaterials used for direct pulp capping and to compare their properties, efficacy, and limitations. Literature published between 2019 and 2024, including systematic reviews, meta-analyses, and clinical studies, was analyzed. The results show that bioceramics and contemporary calcium silicate cements exhibit high bioactivity, enable the formation of a dentin bridge, and present a favorable safety profile. Appropriate material selection, meticulous clinical technique, and effective control of infection and moisture are essential for clinical success. The review also highlights certain limitations, such as the higher cost of new materials, technical requirements, and the lack of long-term clinical data. In conclusion, bioceramics currently represent the best choice for direct pulp capping, and further research should focus on optimizing clinical protocols and evaluating long-term outcomes to ensure predictable, minimally invasive dental care.