Intense blue-green-emitting Eu2+: Ca-3(PO4)(2) and tunable multicolor-emitting Eu2+Mn2+: Ca-3(PO4)(2) phosphors are prepared via a solid-state reaction route. Eu2+-doped orthorhombic Ca-3(PO4)(2) phosphor exhibits a broad emission band in the wavelength range of 400-700 nm with a maximum quantum yield of 56.7%, and the emission peak red-shifts gradually from 479 to 520 nm with increase of Eu2+ doping content. Broad excitation spectrum (250-420 nm) of Eu2+: Ca-3(PO4)(2) matches well with the near-ultraviolet LED chip, indicating its potential applications as tri-color phosphors in white LEDs. Interestingly, Mn2+ co-doping into Eu2+: Ca-3(PO4)(2) leads to its phase transition from orthorhombic to rhombohedral, and subsequently generates tunable multi-color luminescence from green to red via Eu2+ - Mn2+ energy transfer, under 365 nm UV lamp excitation. (C) 2013 Elsevier Ltd. All rights reserved.