Structural rejuvenation of glasses not only provides fundamental insights into their complicated dynamics but also extends their practical applications. However, it is formidably challenging to rejuvenate a glass on very short time scales. Here, we present the first experimental evidence that a specially designed shock compression technique can rapidly rejuvenate metallic glasses to extremely high-enthalpy states within a very short time scale of about 365 ± 8 ns. By controlling the shock stress amplitude, the shock-induced rejuvenation is successfully frozen at different degrees. The underlying structural disordering is quantitatively characterized by the anomalous boson heat capacity peak of glasses. A Deborah number, defined as a competition of time scales between the net structural disordering and the applied loading, is introduced to explain the observed ultrafast rejuvenation phenomena of metallic glasses.