The phosphors of calcium stannate activated with individual trivalent rare-earth element (REE) ions (Neodymium III, Europium III, Terbium III, Dysprosium III, and Samarium III) were synthesized by high-temperature solid-state reaction (SSR), and their characterization and luminescent properties were investigated. The crystal structures and morphologies of the resultant materials were well characterized by experimental techniques such as X-ray powder diffraction (XRD) and environmental scanning electron microscopy (ESEM). The XRD results display that the rare-earths substitution of Calcium II does not change the structure of calcium stannate host. Obviously, the ESEM image exhibits that phosphors aggregate and their particles with irregular shape exist. The calcined powders of the Europium III, Neodymium III, Samarium III, Dysprosium III, and Terbium III ions doped in calcium stannate exhibits bright red, reddish orange, yellowish, orange white, and green light, respectively. Although there is some intrinsic emission ranging from UV to near-infrared (NIR) due to the host lattice, the dominant signals are from the rare-earth sites, with signals characteristic of the trivalent rare-earth states. The emission spectrum from undoped-calcium stannate phosphor is characterized by two broad bands centered at similar to 800 and similar to 950nm. The shapes of the emission bands are different for each dopant. The sharp emission properties show that the calcium stannate is a suitable host for rare-earth ion-doped phosphor material. Furthermore the influence of different rare-earth dopants, that is, Europium III, Neodymium III, Samarium III, Dysprosium III, and Terbium III, on thermally stimulated luminescence (TSL) of calcium stannate phosphor under the beta irradiation was discussed. Among these trivalent rare-earth-doped phosphors samarium-doped material showed maximum TSL sensitivity with favorable glow curve shape.