Novel Mn4+-activated KLaMgWO6 red phosphors with different Mn4+ concentrations were successfully synthesized via a high-temperature solid-state reaction method. The phase formation, microstructure, photoluminescence properties, decay lifetimes and internal quantum efficiency were discussed to analyze the properties of the as-prepared phosphors. The samples belonged to monoclinic crystal system with enough WO6 octahedrons that provided suitable sites for Mn4+ ions. Upon the excitation of 348 nm, KLaMgWO6:Mn4+ phosphors gave bright far-red emission around 696 nm due to the 2Eg→4A2g transition of Mn4+ ions. The critical concentration of Mn4+ was 0.6 mol% and the concentration quenching mechanism belonged to electric multipolar interaction. Besides, the CIE chromaticity coordinates of the KLaMgWO6:0.6%Mn4+ phosphor were (0.7205, 0.2794) which located in deep red range, and its color purity reached up to 96.6%. The KLaMgWO6:0.6%Mn4+ sample also exhibited high internal quantum efficiency of 43%. All of the admirable optical properties indicate that the KLaMgWO6:Mn4+ phosphors can be applied to indoor plant growth illumination.