The phase component, structure and dielectric properties of (Sr,Ca)TiO3 systems were studied. When ST/CT ratio is 7:3, a main crystalline phase (Sr0.7Ca0.3)TiO3 complete solid solution with the ABO(3) perovskite structure is formed, the dielectric properties are improved by a microscale next crystalline phase BNT(Ba6Ti2Nb8O30) with the tungsten bronze structure in the system. The new ceramic materials with excellent dielectric properties (epsilon((20degreesC1MHZ))greater than or equal to250, alpha(c(-55similar to+125degreesC))= -1150ppm/degreesC, tgdelta((20degreesC1MHZ))<5x10(-4), rho(v(20 degrees C100VDC))>= 10(13)Omega.cm) do not contain lead or bismuth, and can be used for Q group multilayer ceramic capacitors.