Copper-doped LiNbO 3 waveguides were prepared by Cu-Li ion-exchange process. Compositional, structural, and optical analyses were performed by secondary ion mass spectrometry, x-ray diffraction, and m-line spectroscopy, respectively. The chemical state of Cu 2+ ions was studied by electron paramagnetic resonance, and the results were correlated with structural modification of the LiNbO 3 matrix. Copper incorporation in the crystal took place under different regimes, and it induced a lattice rearrangement with the formation of new crystalline phases. Cu 2+ ions were surrounded by tetragonally compressed octahedra with rhombic distortions. Cu:LiNbO 3 optical waveguides were formed supporting two optical modes.