Ceramics in (1−x)SrLaAlO4‐xSr2TiO4 system were synthesized in the entire range of 0 ≤ x ≤ 1 by a standard solid‐state reaction method. X‐ray diffraction patterns revealed a single solid solution phase Sr1+xLa1−xAl1−xTixO4 with K2NiF4‐type structure. The cell refinement showed the linear variation of lattice parameters a, c, and cell volume. With increasing x, εr increased from 17.6 to 31.0, whereas τf was tuned from −32 to 122 ppm/oC. The Qf value first increased and then decreased with increasing x due to the result of competition balance between the effect of layer mismatch and interlayer polarization. The degradation of Qf value in the vicinity of x = 0.2 could be attributed to the compositional fluctuation and inhomogeneity originated from the positive mixing enthalpy ΔHmix, which could be confirmed by TEM observation. The best combination of microwave dielectric characteristics was achieved at x = 0.4: εr = 18.5, Qf = 95 000 GHz, τf = −8.9 ppm/oC.