AbstractSugar oximes can be derivatized to yield both the peracetylated oxime and nitrile. The peracetylated oximes do not elute under isothermal (i.e., 200°C) gas chro‐ matography (GC) conditions. When a seven‐component derivatized sugar mixture, as determined by GC, was chromatographed under supercritical fluid chromatography (SFC) conditions with a cyanopropyl capillary column, at least 17 peaks were observed. In an effort to identify the additional derivatization products, the eluates were sub‐ jected to SFC‐FTIR and SFC‐MS. The spectral data indicate that cyclic and acyclic oximes as well as nitrile were formed as part of the derivatization method.