A novel hybrid organic-inorganic photocurable sol-gel material based on tantalum ethoxide and 3-trimethoxysilylpropylmethacrylate has been developed, characterised and used in the fabrication of optical waveguides and three-dimensional woodpile structures employing the single and two-photon polymerisation techniques, respectively. Single mode waveguides operating at 1310 and 1550 nm have been fabricated, optically characterised and their performances correlated to the material formulation. Three-dimensional woodpile structures exhibiting negligible shrinkage have been developed and their remarkable mechanical stability correlated to the molecular structure of the hybrid material. The overall fabrication process of these devices is described and it is shown that the refractive indices of the materials can be tailored by a precise control of the material composition allowing the successful fabrication of performing single mode waveguides. (C) 2010 Elsevier B.V. All rights reserved.