Ageing vessels are critical to the sensory maturation of Baijiu, yet the interfacial material processes by which traditional ceramics modulate liquor chemistry remain insufficiently defined. Here, Zisha and ceramic-clay particles with distinct aluminosilicate frameworks, mineral compositions, and pore structures were investigated to elucidate their roles in sauce-flavor Baijiu ageing. Ceramic characterization was combined with elemental and volatile analyses using ICP-MS, GC-MS, and GC-IMS. The results showed that pore development in Zisha was primarily governed by fluxing metal oxides and the Si/Al framework, whereas metal-ion migration into Baijiu was regulated by the SiO₂-rich matrix, pore accessibility, and trace elemental composition. Metal elements exhibited reversible interfacial exchange rather than simple leaching, revealing a dynamic metal-ion cycling process during ageing. This process was associated with selective remodeling of the volatile profile. Compared with ceramic-clay particles, Zisha promoted the accumulation of acetophenone, 3-pentanone, and pyrazine derivatives while reducing dimethyl disulfide and heptanal. Sensory evaluation of Baijiu aged in ceramic jars further validated these findings. These findings identify Zisha ceramics as active material–flavour interfaces and provide a mechanistic basis for the rational design of ceramic ageing vessels to direct Baijiu flavour maturation.