To study the dissolution mechanism of gangue, dissolution characteristics of the gangue samples calcined at different temperatures in alkaline solutions and alkali metal silicate solutions with respect to Si and Al ions were analyzed by identical coupled plasma optical emission spectroscopy (ICP). The results show that the extent of dissolution of Al and Si varies with calcination temperature. It shows that the samples have a higher degree of dissolution in NaOH than in KOH medium. Si and Al appear to have synchro-dissolution behavior in alkaline solution, which means that Si and Al could dissolve from the mineral surface in certain linked forms. The result that a higher degree of dissolution exists in sodium silicate solution and a lower degree of dissolution exists in sodium-potassium silicate solution of Al is proved by the ²⁹Si NMR spectra and the mean connectivity degree of these alkali metal silicate solutions.