Crystal structure and microwave dielectric properties of Ca [(Li1/3Nb2/3) 0.95Zr0.05]O3−δ−xTiO2(0≤x≤0.1) ceramics were investigated. A single phase with orthorhombic perovskite structure was obtained at x=0.02~0.1. With an increasing of Ti4+ content, the Qf value decreased due to a decrease of the degree of B-site 1:2 ordering. However, the τf value increased from-14.7ppm /°C to-6.9ppm/°C. When x=0.04, the optimum microwave dielectric properties: εr=31.1, Qf =21640GHz and τf =−8.8 ppm/°C.