CaSiO 3 :Eu 3+ (1–5mol%) red emitting phosphors have been synthesized by a low-temperature solution combustion method. The phosphors have been well characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and optical spectroscopy. PXRD patterns reveal monoclinic CaSiO 3 phase can be obtained at 900°C. The SEM micrographs show the crystallites with irregular shape, mostly angular. Upon 254nm excitation, the phosphor show characteristic fluorescence 5 D 0 → 7 F J (J=0, 1, 2, 3, 4) of the Eu 3+ ions. The electronic transition located at 614nm corresponding to 5 D 0 → 7 F 2 of Eu 3+ ions, which is stronger than the magnetic dipole transition located at 593nm corresponding to 5 D 0 → 7 F 1 of Eu 3+ ions. Different pathways involved in emission process have been studied. Concentration quenching has been observed for Eu 3+ concentration>4mol%. UV–visible absorption shows an intense band at 240nm in undoped and 270nm in Eu 3+ doped CaSiO 3 which is attributed to oxygen to silicon (O–Si) ligand-to-metal charge-transfer (LMCT) band in the SiO 3 2− group. The optical energy band gap is widened with increase of Eu 3+ ion dopant.