We examined copper (Cu) absorption, distribution and toxicity and the role of a silicon (Si) supplementation in the bamboo Phyllostachys fastuosa. Bamboos were maintained in hydroponics for 4 months and submitted to two different Cu (1.5 and 100 μm Cu(2+)) and Si (0 and 1.1 mM) concentrations. Cu and Si partitioning and Cu speciation were investigated by chemical analysis, microscopic and spectroscopic techniques. Copper was present as Cu(I) and Cu(II) depending on plant parts. Bamboo mainly coped with high Cu exposure by: (i) high Cu sequestration in the root (ii) Cu(II) binding to amino and carboxyl ligands in roots, and (iii) Cu(I) complexation with both organic and inorganic sulfur ligands in stems and leaves. Silicon supplementation decreased the visible damage induced by high Cu exposure and modified Cu speciation in the leaves where a higher proportion of Cu was present as inorganic Cu(I)S compounds, which may be less toxic.