The synthesis behavior of nanoporous silica aerogel in the macroporous ceramic structure was observed using TEOS as a source material and glycerol as a dry control chemical additive (DCCA). Silica aerogel in the macroporous ceramic structure was synthesized via sono-gel process using hexamethyldiazane (HMDS) as a modification agent and n-hexane as a main solvent. The wet gel with a modified surface was dried at under ambient pressure. The addition of glycerol appears to give the wet gel a more homogeneous microstructure. However, glycerol also retarded the rate of surface modification and solvent exchange. Silica aerogel completely filled the macroporous ceramic structure without defect in the condition of surface modification (20% HMDS/nhexane at 36hr).