We report the microstructures and dielectric properties of Ca1-xSrxCu3Ti4O12 (C1-xSxCTO, 0≤x≤1) ceramics sintered at the various sintering temperatures ranging from 1000 to 1060˚C in air. The linear increase in lattice parameter in C1-xSxCTO (0≤x≤1) ceramics is observable for the full range of substitution. However, the second phases of SrTiO3 and CuO start to occur from the composition of x=0.8, implying that a stoichiometric SrCu3Ti4O12 (SCTO) compound may not exist. While the C0.6S0.4CTO and C0.4S0.6CTiO samples exhibit relatively lower dielectric constant (εr) of ∼40,000 below 1 kHz, the CaCu3Ti4O12 (CCTO) and SCTO show the extremely high εr values of ~120,000 and ∼180,000, respectively. Complex impedance (Z*) and modulus (M*) spectroscopy revealed that the capacitance (C) and resistivity (ρ) values of grain boundary in all samples are much higher than those of grains.