In a process for fabrication of an optical slot waveguide on silicon, a thin single-crystal silicon film is deposited on a substrate covered with an insulating buried layer; a local thermal oxidation is carried out over the entire depth of the thin single-crystal silicon film in order to form an insulating oxidized strip extending along the desired path of the waveguide; an insulating or semi-insulating layer is deposited on the silicon film; two openings having vertical sidewalls are excavated over the entire thickness of this insulating or semi-insulating layer, said openings being separated by a narrow gap constituting an insulating or semi-insulating vertical wall that will be the material of the slot; single-crystal silicon is grown in the openings and right to the edges of the insulating or semi-insulating wall; and then the upper part of the silicon is etched in order to complete the geometry of the waveguide.