Within Mn-activated phosphors, the oxidation state of Mn dopant strongly depends on the structural features of the host lattice. This paper reported a new polymorph of CsMg(PO 3 ) 3 (CMP) with a complicated three-dimensional (3D) framework of [Mg(PO 3 ) 3 ] ∞ that is constructed by MgO 6 octahedra and 1D infinite [PO 3 ] ∞ chains. Then we prepared a series of red phosphors CsMg 1−x (PO 3 ) 3 :xMn 2+ (CMP:xMn 2+ ) by high temperature solid state reactions in the open air. Powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) studies revealed the single Mn 2+ -oxidation. Under 404 nm light exciting, CMP:0.2Mn 2+ can emit single-band emission at around 630 nm with full-width at half-maximum (fwhm) of 70 nm. Besides, CMP:0.2Mn 2+ possesses excellent thermostability up to 450 K. These features indicate that CMP:0.2Mn 2+ is suitable to be used for LED backlight display. Moreover, this work suggests that a host lattice with suitable structure feature can form single Mn 2+ -oxidation and is rigid enough to protect Mn 2+ from being oxidized by O 2 at high temperature.