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A novel phosphor LiBaPO4 doped with rare earths Eu and Dy prepared by high temperature solid-state reaction method is reported. The phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL). The emission and excitation spectra of these materials were measured at room temperature with a spectrofluorophotometer. The excitation spectra of LiBaPO4:Eu3+ phosphor can be efficiently excited by 394 nm, which is matched well with the emission wavelength of near-UV light-emitting diode (LED) chip. PL properties of Eu3+-doped LiBaPO4 exhibited the characteristic red emission coming from 5D0 → 7 F1 (593 nm) and 5D0 → 7 F2 (617 nm) electronic transitions with color co-ordinations of (0.680, 0.315). The results demonstrated that LiBaPO4:Eu3+ is a potential red-emitting phosphor for near-UV LEDs. Emission spectra of LiBaPO4:Dy3+ phosphors showed efficient blue (481 nm) and yellow (574 nm) bands, which originated from 4 F9/2 → 6H15/2 and 4 F9/2 → 6H13/2 transitions of the Dy3+ ion, respectively. The 574 nm line is more intense than the 481 nm lines, which indicates that the site Dy3+ is located with low symmetry. This article summarizes fundamentals and possible applications of optically useful inorganic phosphates with visible photoluminescence of Eu3+ and Dy3+ ions. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]