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A series of new red-emitting BaCa1-2xBO3F:xEu3+, xM+ (M=Li, Na, K) phosphors were synthesized by the solid-reaction method.X-ray diffraction (XRD), diffuse reflection (UV-vis) and photoluminescence spectra were utilized to characterize the crystallization process,structure and luminescence properties of the as-synthesized phosphors. The XRD results indicated that the sample began to crystallize at 800 ℃,and single-phase BaCaBO3F was fully obtained after annealing at 1000 C. The charge compensated behaviors were investigated in this paper by considering different cations like Li+, Na+ and K- acting as the charge compensator. The as-prepared phosphors had better emission properties, and the two characteristic emission lines peaking at 590 and 615 nm could be obtained upon 394, 463 and 532 nm excitation with the chromaticity coordinates of (0.596, 0.391), which were due to 5D0-7F1 and 5D0-TF2 transitions of Eu3+ ions. Further, the concentration quenching and corresponding luminescence mechanisms of BaCa1-2xBO3F:xEu3+, xNa+ phosphors were also discussed.