We present an extensive theoretical analysis of reverse-symmetry waveguides with special focus on their potential application as sensor components in aqueous media and demonstrate a novel method for fabrication of such waveguides. The principle of reverse symmetry is based on making the refractive index of the waveguide substrate less than the refractive index of the medium covering the waveguiding film (n(water) = 1.33). This is opposed to the conventional waveguide geometry, where the substrate is usually glass or polymers with refractive indices of approximate to1.5. The reverse configuration has the advantage of deeper penetration of the evanescent electromagnetic field into the cover medium, theoretically permitting higher sensitivity to analytes compared to traditional waveguide designs. We present calculated sensitivities and probing depths of conventional and reverse-symmetry waveguides and describe schemes for easy implementation of reverse symmetry. Polymer waveguides are demonstrated to be candidates for cheap, mass-producible reverse-symmetry sensor modules. The grating-coupled waveguiding films of controlled thickness are produced by soft lithography. The resulting films are combined with air-grooved polymer supports to form freestanding single-material polymer waveguides of reverse symmetry capable of guiding light.