Series microwave dielectric ceramics with the composition of Ba 4 LiNb 3−x Sb x O 12 (0≤x≤3) were prepared by the solid state reaction method. The phase transformation, microstructure and microwave dielectric properties of ceramics were investigated by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and a network analyzer. The sequence of structure transformation was detected with increasing x values; Hexagonal (0≤x≤0.75)→Hexagonal+Cubic (0.75<x≤1.25)→Cubic (1.25<x≤3). The microwave dielectric properties were improved through substituting Sb for Nb. Especially, the temperature coefficient of resonate frequency (τ f ) can be tailored to zero. Based on the overall performance, the best result was obtained for the Ba 4 LiNb 2 SbO 12 (ε r =24.6, Qf=52,100GHz, τ f =0ppm/°C), indicating that the Ba 4 LiNb 3−x Sb x O 12 ceramics are suited for the dielectric resonate applications.