The crack-free silica monolith with macropores and mesopores has successfully been achieved in the presence of citric acid as nonsurfactant via sol-gel reactions of tetramethoxysilane (TMOS). Citric acid was removed by calcination to afford monolithic bodies with high specific surface area of 648 m(2)/g, pore volume of 0.9 cm(3)/g. Poly (ethyl glycol) has been used together with citric acid to control the particle aggregation and internal structure. Macropores in the micrometer range originate from the spinodal phase separation and gelation kinetics. Textural mesopores in the 2-8 nm range are controlled through adding citric acid and postsynthesis treatment in ammonia solution. By employing the glycerol as drying control chemical additives (DCCA), cracks of the materials can be successfully avoided.