Dehua kiln was a famous folk kiln in Southern China with a long history. The surfaces of Dehua white porcelain unearthed from the kiln site are generally attached with yellow induration. Based on a comprehensive analysis of a Southern Song white porcelain sample with yellow induration, this study investigated the deterioration mechanism of the glaze and the formation of induration deposits in the soil environment of Dehua. The analytical methods used include optical microscopy (OM), energy dispersive X-ray fluorescence (EDXRF) spectrometry, micro-Raman (μ-Raman) spectrometry and scanning electron microscopy-energy dispersive spectrometry (SEM-EDS). The results indicate that the Southern Song Dehua glaze is a transparent calcium-alkali glaze. The main degradation processes in an acidic soil environment include ion exchange and network dissolution. Silicon released during network dissolution subsequently condensed to form silica gel on the glaze surface, and variations in local pH led to the development of two special microstructures of silica gel. The yellow induration layer was formed through the condensation of silica gel and inorganic soil colloids via electrostatic attraction and intermolecular force.