The objective of the study is to investigate the effect of released silicon (Si) and aluminum (Al) during the formation of volcanic ash soil on the content of Si in groundwater on Jeju Island. Volcanic ash soils in Jeju Island were formed from pyroclastic materials that originated from basalt. We sampled four profiles, including basaltic bedrock of each soil series with large variations in elevation (160–320 m) and mean annual precipitation (MAP; 1,800–2,600 mm). The soil and bedrock minerals were analyzed for weathering of volcanic ash soils related to mineralogical transformations and mobility of Si and Al. Andisols (above 2,000 mm MAP) were dominantly composed of allophane and gibbsite. In Andisols used in the study, 10–70% of Si was lost, whereas the amount of Al was relatively conserved. This is because Al forms Al-humus complex and Andisols contain allophane. In contrast, non-Andisols located at low altitude with lower than 1,800 mm MAP were enriched with considerable amounts of Si and Al, because non-Andisols have crystalline clay minerals and quartz. These results indicate that Andisols, which are widely distributed in Jeju Island, may play an important role in contributing to the high concentration of dissolved Si in the groundwater.