It is a tough challenge to understand the mutual interactions among various components in aqueous solutions of inorganic mixed with organic solutes. The hydration number, n(h), and critical hydration number, ncr, determined by the measurements of glass transition of the solutions, in conjunction with tracing the change in local water structure, can provide some insights into the complicated interplays in such a mixture. Here, the n(h) and n(cr) for aqueous solutions of glycerol, various chlorides, and mixtures of glycerol with a chloride are determined. The ratio of n(cr)/n(h) measures 4 for glycerol and 1.7 for all the chlorides, and for mixtures of glycerol with all of the chlorides except ZnCl2, it falls within these two extremes. Glycerol content dependence of n(h) and n(cr) reveals a rich and interesting scenario of mutual effects therein, in particular, the glycerols replacement and sharing of hydration water with salt. In the case of ZnCl2, at most, one hydration water molecule is replaced by glycerol, and the excess glycerol molecules continuously reduce the number of glycerol molecules that share hydration water with ZnCl2. Our results can help establish a pathway for the investigation of interactions among the organic and inorganic components in aqueous solutions, which is desirable for many applications.