Abstract: The (14-x)SrCO3xCaCO324CuO system was investigated by means of differential thermal analysis (DTA) technique combined with the powder Xray diffraction (XRD) technique, and the relationship of its thermal behavior with the synthesis of spin-ladder compound Sr14-xCaxCu24O41 was first analyzed in detail. It is found that the DTA curve (x≤5.6) exhibits two endothermic peaks and could be divided into three reaction stages, corresponding to the solid state reaction to synthesize single-phase Sr14-xCaxCu24O41. The DTA curve (x≥8.4) shows three big endothermic peaks below 1000 ℃. The intensity and the position of the first endothermic peak around 800 ℃ is depending on the content of CaCO3 in the system， while the third endothermic peak is the crucial factor of the synthesis of single-phase compound.