Roots extract of Rhodiola rosea L. is the source of important commercial preparations widely used throughout Europe, Asia, and the USA. Phytochemical investigation of the roots of Rhodiola rosea afforded 17 compounds, belonging to the phenylalkanoids and monoterpene analogues. Their structures were determined by spectroscopic and chemical methods. Rhodioloside F ( 1) was found to be new. The X-ray crystallographic study on salidroside ( 7) and the complete NMR data of 5 (mongrhoside) and 1A [(-)-rosiridol] are also described.