Two-photon photopolymerization of inorganic-organic hybrid materials permits the generation of complex-shaped three-dimensional microstructures at submicrometer resolution of structural elements. Due to their favorable optical, chemical and thermal properties these materials are particularly useful for photonic microdevice fabrication. Focussing ultrashort pulsed visible light into a modified commercially available polysiloxane polymer a Sydney Opera House design and a series of woodpile-type photonic crystals were fabricated. Fourier transform infrared spectroscopy revealed photonic stop gaps in the stacking direction at wavelengths varying from 6 to 4lm upon reduction of the woodpile rod size. The structures allowed for the observation of higher-order stop gaps.