Crystal structure and microwave dielectric properties of (Ca1-xPrx) [(Li1/3Nb2/3)0.95Zr0.15]3+δ (0.0≤x≤0.2, CPLNZ) ceramics were investigated. A single phase with orthorhombic perovskite structure was obtained at x=0.0~0.08. With an increase of Pr3+ content, the quality factor value firstly increased, and then began to decrease at x=0.06 due to a decrease of the degree of B-site 1:2 ordering. The variation of τf with tolerance factor was discussed. When x=0.06, the optimum microwave dielectric properties: the permittivity is 33.2, the quality factor is 17120 GHz，and the temperature coefficient of resonator frequency is −5.7×10−6/°C.