We report the first spectroscopic detection of perdeuterated 1-oxadisulfane, DSOD, generated in a radio-frequency plasma of D 2 S and D 2 O. The chain molecule DSOD produces a perpendicular-type spectrum, with well-known spectral features encountered in previous studies of geometrically related molecules, such as compact Q-branches, which are clearly recognizable. The arrangement of the transitions shaping the Q-branches usually provides sufficient proof for a clear-cut detection of a chain molecule such as DSOD. Guided by quantum chemical calculations, we have located the band center of the rQ2-branch of DSOD in the frequency region near 466.5GHz using the Cologne terahertz spectrometer. This rQ2-branch displays both b- and c-type spectra, quite analogous to the behavior of the corresponding rQ2-branch of HSOH. In addition, we have been able to detect an internal rotational splitting of ∼0.5MHz for c-type transitions of the rQ0-branch, which lends independent support to our present assignment. From the measurements performed on Q-branches, we derive the following differences in rotational constants: A−(B+C)/2=93331.001(15)MHz, and (B−C)/4=172.95923(29)MHz, in excellent agreement with theoretical predictions.