PET fabric with highly hydrophilic surface was obtained by microwave-assisted, nonaqueous glycolysis under alkali condition. Surface hydrophilicity was measured by water drop test, vertical wicking test, and contact angle measurement. At 120 s of irradiation, the glycolyzed PET showed instantaneous wetting with a low level of alkali concentration, such as 0.1% NaOH. DSC and SEM analyses were used to investigate thermal and topological characteristics of the glycolyzed PET. Depending on the required hydrophilicity, the level of alkali and irradiation time must be adjusted. Use of microwave-assisted modification could reduce the treatment time to less than 180 s from 1 to 2 h in a conventional dyeing machine treatment, allowing considerable savings in energy and processing costs.