Crystal structure and properties of Sr₁₁Mo₄O₂₃ treated at 1100 and 1400 °C were studied via synchrotron X-ray powder diffraction and thermogravimetric analysis, coupled with mass spectrometry. Synchrotron studies reveal the crystallographic effect of the annealing temperature, showing that the lowest-temperature phase must be defined in a triclinic symmetry, in contrast to the cubic one obtained at 1400 °C. The mass spectrometry allowed the identification of the released compounds during the thermogravimetric analysis, thus unveiling the physicochemical behavior of the sample during the heating process. Furthermore, an aging analysis was made, confirming the superior stability of this sample when it is treated at 1400 °C. Finally, an optimized sintering procedure allowed us to obtain a superior density and hence the highest conductivity measured so far for this system.