Abstract Red phosphors of Li-doped CaTiO3:Eu3+ that enhance photoluminescence have been synthesized by a solid-state method, and their structure and morphology were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The luminescence property was measured using photoluminescence excitation (PLE) and photoluminescence (PL) spectra, respectively. The effect of sintered temperature and Eu3+ and Li+ concentration in as-prepared series phosphors was studied. Results indicate that the optimal luminescence properties of CaTiO3:Eu3+ (CTE) phosphors are typically obtained at 1300°C with 12mol% of Eu3+ concentration, and the emission intensity can be greatly enhanced by the incorporation of Li+ into the CTE phosphors, attributing that Li not only compensates positive charge defect by replacement of Ca2+ with Eu3+, but also plays a role of flux, which could enhance the crystallinity of the phosphors. The intensity of the optimal Li-doped CaTiO3:Eu3+ phosphor (CLTE) is 2.3 times of that of CTE. PL spectrum showed that CLTE phosphor was efficiently excited by near-ultraviolet light at wavelength around 398nm and emitted intensive red light with a peak around 616nm corresponding to the 5D0→7F2 transition of Eu3+. Furthermore, this phosphor has very good thermal stability and high color purity, implying the potential to be a promising red phosphor in white light emitting diodes.