Grapevine canes, a pruning-derived by-product, possess a great amount of bioactive (poly)phenolic compounds belonging to different chemical classes, thus, having a good potential for further valorization. However, in order to properly design valorization strategies, the precise chemical composition of this material has to be known. Up to now, this chemical characterization has been based on analysis of different groups of components individually, due to difficulties related to their huge chemical variability. In this work, a comprehensive two-dimensional liquid chromatography-based method (LC x LC) is developed to obtain the profiles of (poly)phenolic compounds present in grapevine canes from several varieties. Three different set-ups have been tested and compared; the combination of diol and C-18 columns produced the best results, allowing the characterization of the (poly)phenolic profile in around 80 min. This way, 81 different components were detected in the samples; most of them could be tentatively assigned using the information provided by the DAD and MS detectors employed. Indeed, it has been possible to detect in a single run components belonging to stilbenoids, procyanidins and prodelphinidins of varying degrees of polymerization, some of them not formerly described in this natural source. The method has shown extremely good separation capabilities, and is characterized by high effective peak capacity (842) and orthogonality (A(0) = 78%). The obtained results demonstrate that Vitis vinifera L. canes may retain a great potential to be used as an underexploited natural source of bioactive compounds, with potential applications in different fields. (C) 2017 Elsevier B.V. All rights reserved.Regular 2015FONDECYTFONDECYT