We experimentally demonstrate a novel silicon waveguide structure for guiding and confining light in nanometer-wide low-refractive-index material. The optical field in the low-index material is enhanced because of the discontinuity of the electric field at high-index-contrast interfaces. We measure a 30% reduction of the effective index of light propagating in the novel structure due to the presence of the nanometer-wide low-index region, evidencing the guiding and confinement of light in the low-index material. We fabricate ring resonators based on the structure and show that the structure can be implemented in highly integrated photonics.