Cyclomaltodextrin glucanotransferase (CGTase) has been efficiently applied to complexation of vitamin E in brown rice (Rice) and unpolished six-row barley (Barley). The results are shown as follows. ① Rice showed a higher vitamin E content than that of Barley, whereas the composition and contents of tocopherol and tocotrienol of Rice were similar to those of Barley. ② Production of cyclodextrin (CD) from Rice with CGTase showed a tendency to increase in cultivars having lower amylose content. ③ CD was produced from Rice and Barley with CGTase below 30% ethanol concentration. The composition of CD depended on the ethanol concentration of and raw material used. ④ The vitamin E-CD complex was produced below 30% of ethanol concentration by treating Rice and Barley with CGTase, and the content of vitamin E in the complex increased with increasing in ethanol concentration. ⑤ The complex exhibited a high water-solubility (about 90% or higher) below 30% ethanol concentration. ⑥ The complex produced in the presence of ethanol exhibited that the antioxidant capacity increased with increasing ethanol concentration to 30%.