K3MoOF7:Mn4+ was synthesized through a facile two‐step solid‐state synthesis route without using HF. The first step was carried out in copper ampules, which were shut by welding, followed by the second step, a ball milling experiment. The sample was characterized by single‐crystal and powder X‐ray diffraction, EDX, and luminescence spectroscopy. K3MoOF7 crystallizes in the triclinic space group P1 (no. 2). It features [MoOF5]- units as a main structural motif. At room temperature, seven emission lines are noticeable. The maximum emission line is located at λ[lambda]max = 627 nm. CIE1931 coordinates could be determined to 0.690(1) and 0.310(1) for x and y, respectively. A luminous efficacy of radiation (LER) of 218 lm Wopt-1 was achieved. Furthermore, temperature dependent luminescence measurements in the range of 25 °C to 100 °C were conducted.