Double-perovskite Ba2Zn1−xMoO6:xEu3+ (x=0, 0.02, 0.04, 0.06, 0.08, 0.1) orange–red emitting phosphors were synthesized by using the sol–gel method. The crystalline structure and photoluminescence properties of the phosphors were investigated. The X-ray diffraction (XRD) patterns indicate that the structure of matrix Ba2ZnMoO6 is cubic double-perovskite with space group Fm-3m. The Ba2ZnMoO6:Eu3+ phosphors present an intense broad charge transfer (CT) band absorption in near UV range (370–410nm), which attributes to the charge transfer state of MoO6, and performs orange–red emission of Eu3+ (5D0→7F1 transition) at around 596nm. A low concentration quenching occurs in Ba2ZnMoO6:Eu3+ and the optimal doping concentration is about 6mol%. The Ba2ZnMoO6:Eu3+ phosphors are considered to be a promising orange–red emitting phosphor for near ultraviolet GaN-based white light emitting diode.