<p>This study investigates the structure–property relationship in Jin-Yuan period (1115–1368 CE) oil-spot glazes from the archaeological site of Jining Lu to elucidate the scientific principles governing their distinctive coloration patterns. Through multi-scale characterization of 20 ceramic fragments using ultra-depth microscopy, SEM–EDS (Scanning Electron Microscopy-Energy Dispersive Spectrometer), XRD (X-ray Diffraction), WDXRF (Wavelength-dispersive X-ray fluorescence) and XPS (X-ray photoelectron spectrometer) , we establish fundamental correlations between processing conditions, crystalline phases, and optical properties. The ceramic bodies exhibit a characteristic high-alumina composition (Al₂O₃: 24.5–34.0 wt%), reflecting regional clay sources and manufacturing traditions. Glaze chemistry reveals intentional flux optimization, with high CaO content (4.5–7.2 wt%) and Fe₂O₃ enrichment facilitating liquid-phase sintering. Most significantly, we demonstrate that the silver/red dichroism is predominantly governed by atmospheric conditions modulating Fe²⁺/Fe³⁺ ratios and crystal polymorphism:(i) In a strong oxidizing atmosphere, vapor-phase deposition produces specular α-Fe₂O₃ (hematite)&#xa0;microcrystals (2–5&#xa0;μm), yielding metallic luster; (ii) In a weak reducing-weak oxidizing atmosphere, co-precipitation of dendritic α-Fe₂O₃&#xa0;and magnetoelectric ε-Fe₂O₃ (luogufengite)&#xa0;is promoted, generating distinct chromatic contrast. These findings provide mechanistic insights into ancient craftsmen’s empirical control of phase transformations in iron-oxide systems.</p>