Aim: Calcium silicate-based materials are hydraulic self-setting materials with physico-chemical properties suitable for endodontic surgery and good biological/clinical outcomes. The study aim was to evaluate the bio-properties (biointeractivity and apatite-forming ability) and selected physical properties (porosity, water sorption, solubility, and setting time) of Biodentine, a tricalcium silicate material for endodontics and restorative dentistry, compared to that of ProRoot MTA (Mineral Trioxide Aggregate) as gold standard material. Methods: Biodentine and ProRoot MTA pastes were prepared and analyzed for calcium release and alkalinizing activity (3 h–28 days), setting time, water sorption, porosity, solubility, surface microstructure and composition, and apatite-forming ability in simulated body fluid. Results: Biodentine showed higher calcium release, alkalinizing activity, and solubility but higher open and apparent porosity, water sorption, and a markedly shorter setting time. Calcium phosphate (CaP) deposits were noted on material surfaces after short ageing times. A CaP coating composed of spherulites was detected after 28 days. The thickness, continuity, and Ca/P ratio of the coating differed markedly between the materials. Biodentine showed a coating composed by denser but smaller spherulites, while ProRoot MTA showed large but less dense aggregates of spherulitic deposits. Conclusions: Biodentine showed a pronounced ability to release calcium and extended alkalinizing activity interlinked with its noticeable porosity, water sorption, and solubility: open porosities provide a broad wet biointeractive surface for the release of the calcium and hydroxyl ions involved in the formation of a CaP mineral. Biodentine is a biointeractive tricalcium silicate material with interesting chemical-physical properties and represents a fast-setting alternative to the conventional calcium silicate MTA-like cements.