This study aims to optimize quantitative X-ray diffraction (XRD) mineralogical analysis of the minority phases in clinker. The proposed method consists of applying Rietveld quantitative refinement to the XRD patterns for both clinker and the insoluble residue remaining after it is attacked with methanol and salicylic acid (Takashima method). The method was tested with industrial clinker and the same material after modifying its mineralogy by refiring at 1500°C followed by slow cooling. The findings showed that the C4AF/C3A ratios for quickly and gradually cooled clinker were much higher when the clinker diffractograms were refined with the Rietveld procedure than when the proposed method was used. The proportion of C3A found with the proposed method was ≈2.8-fold higher than when Rietveld only was applied to the diffractograms for clinkers. Taken together, the refinement data for the two materials (clinker and Takashima residua) revealed that Rietveld quantitative XRD applied to clinker underestimates the low C3A content. These findings are supported by postsulfate attack durability studies conducted on cements prepared with the two clinkers.