In this contribution we report on the preliminary results of synthesis and characterization of both planar and strip-loaded waveguides on silicon substrates. All the layers (buffer, guiding and cladding) have been grown by one step spin-coating process using hybrid organic/inorganic sol-gel route. Their thickness ranges from less than 1 μm, for the cladding layer, up to 4 μm, for the buffer one. The refractive index of the different planar waveguides were measured by means of m-line technique. Layer interfaces have been investigated with secondary ion mass spectroscopy (SIMS). Photolithography and reactive ion etching (RIE) technique have been employed to pattern the strip-loaded structures. Optical and scanning electron microscopy analysis was performed to evaluate their shape. Preliminary longitudinal transmission measurements for strip-loaded waveguides are also reported.