The development of new efficient and environmental-friendly inorganic phosphors is highly important for phosphor-converted white light-emitting diodes and optoelectronic displays. In this paper, we report a novel and simple one-step solid-state reaction to synthesize lead-free cesium copper halide Cs3Cu2Br5 powders with bright blue emission around 460 nm. The preparation process is performed at low calcination temperatures (290–320 °C) and requires no complex apparatus, reagents, or techniques, and thus it holds great potential for mass production of halide emitters. The Cs3Cu2Br5 powder phosphors are characterized by X-ray diffraction, field-emission scanning electron microscopy, energy dispersive X-ray spectroscopy, photoluminescence excitation and emission spectroscopy, CIE color coordinates, color purity, photoluminescence quantum yield, and temperature-dependent emission spectra. The effect of calcination temperature on the photoluminescence properties of the as-prepared Cs3Cu2Br5 blue phosphors has been investigated and the air-stability property has also been discussed. Impressively, Cs3Cu2Br5 blue phosphors show outstanding stability toward air exposure exceeding one month (30 days). Our work will open a new and simple approach to obtain excellent halide emitters for future solid-state lighting and displays.