Because of the health implications of resveratrol and piceid, which are widely present in foods, we focused our attention on the development of a highly efficient methodology for their characterization and measurement. On the basis of our experience in capillary electrophoresis for separation of polyphenolic compounds, we developed a general analytical method for piceid identification which was also applicable to complex natural mixtures such as red wine. In view of its very limited availability from natural sources, we first directed our attention to the development of a synthetic route suitable to produce an adequate amount of polydatin (piceid or resveratrol 3-O-beta-D-glucopyranoside). The latter was synthesized by a new one-step procedure which afforded the expected product in a good yield. The studied compounds were also investigated for their stability to UV irradiation.