The unimolecular decomposition of CH3CH2OH has been investigated at the G2M (RCC2) level of theory. The decomposition reaction was found to be dependent strongly on pressure and temperature. Among the eight product channels identified, the H2O-elimination process (1) via a four-member-ring transition state is dominant below 10 atm in the temperature range of 700-2500 K. At the high-pressure limit and over 1500 K, cleavage of the C-C bond by reaction (2) producing CH3+CH2OH is predicted to be dominant while the CH3CH2+OH channel (8) also becomes competitive. The predicted high-pressure rate constants for the two major product channels can be given by k(1)=7.0x10(13) exp(-34 200/T) and k(2)=3.7x10(26) T-2.95 exp(-45 600/T) s(-1), which compare reasonably with earlier data and with our preliminary experimental result obtained in a shock tube and static cell study. At the internal energy corresponding to the O(D-1)+C2H6 reaction (140.7 kcal/mol above C2H5OH), the predicted branching ratios for the production of CH3, C2H5, and H-2 are in qualitative agreement with the result of a recent cross-molecular beam experiment.