Lath-shaped and highly crystalline trioctahedral smectites were synthesized under hydrothermal conditions. The quenched glasses with stoichiometrically dehydrated Na-smectite compositions were treated at (a) 500℃ and 100 MPa for 1 and 11 days; and (b) 300℃ and 100 MPa for 7 days. The crystallinity and particle size of products were dependent on the chemical composition of the starting glass, synthetic temperature and duration of hydrothermal treatment. The high structural ordering and large dimensions of the products were confirmed from the sharpness of XRD peaks; and hydration behavior under controlled relative humidity. Transmission electron microscopy was also performed for the characterization of the particle size of product. Particle sizes vary from ca. 10 nm to a few μm by changing the chemical compositions of the starting materials. The product with the highest structural ordering and largest dimension was obtained from Na0.33(Mg1.83Al0.67)Si4O11 glass treated at 500℃ and 100 MPa for 1 day. The obtained results also confirmed the metastability and compositional dependency in the formation of highly crystalline trioctahedral smectite at hydrothermal conditions. Lath-shaped and highly crystalline trioctahedral smectites were synthesized under hydrothermal conditions. The quenched glasses with stoichiometrically dehydrated Na-smectite compositions were treated at (a) 500 ° C and 100 MPa for 1 and 11 days; and (b) 300 ° C and 100 MPa for 7 days. The crystallinity and particle size of products were dependent on the chemical composition of the starting glass, synthetic temperature and duration of hydrothermal treatment. The high structural ordering and large dimensions of the products were confirmed from the sharpness of XRD peaks; and hydration behavior under controlled relative humidity. Transmission electron microscopy was also performed for the characterization of the particle size of product. Particle sizes vary from ca. 10 nm to a few μm by changing the chemical compositions of the starting materials. The product with the highest structural ordering and largest dimension was obtained from Na0.33 (Mg1.83Al0.67) Si4O11 glass treated at 500 ℃ and 100 MPa for 1 day. The obtained results also confirmed the metastability and compositional dependency in the formation of highly crystalline trioctahedral smectite at hydrothermal conditions.