We demonstrate a swift ion-beam irradiation procedure based on electronic (not nuclear) excitation to generate a large index jump step-like optical waveguide (Δn0 ≈ 0.2, Δne ≈ 0.1) in LiNbO3. The method uses medium-mass ions with a kinetic energy high enough to assure that their electronic stopping power Se(z) reaches a maximum value close to the amorphous (latent) track threshold inside the crystal. Fluorine ions of 20 and 22 MeV and fluences in the range (1–30)×1014 are used for this work. A buried amorphous layer having a low refractive index (2.10 at a wavelength of 633 nm) is then generated at a controlled depth in LiNbO3, whose thickness is also tuned by irradiation fluence. The layer left at the surface remains crystalline and constitutes the core of the optical waveguide which, moreover, is several microns far from the end of the ion range. The waveguides show, after annealing at 300 °C, low propagation losses ( ≈ 1 dB/cm) and a high second-harmonic generation coefficient (50%–80% of that for bulk unirradiated LiNbO3, depending on the fluence). The formation and structure of the amorphous layer has been monitored by additional Rutherford backscattering/channeling experiments.