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In this study, we demonstrate the synthesis of the hetero-dialkaline hexafluorosilicate red phosphor KNaSiF6:Mn4+ by etching Si wafers in a HF/KMnO4/NaMnO4∙H2O mixed solution. The X-ray diffraction analysis indicates that the synthesized phosphor has an orthorhombic structure with the space group D2h16 — Pnma. The luminescence properties of the phosphor are studied by photoluminescence (PL) analysis, PL excitation spectroscopy, and luminescence lifetime measurements, and are found to be intermediate of those of homo-dialkaline K2SiF6:Mn4+ and Na2SiF6:Mn4+ red phosphors. [ABSTRACT FROM AUTHOR]