The suitability of ormosils as photonic materials was investigated. Vinyl and phenyl silicates were synthesised below 100°C. A detailed assignment of mid-infrared vibrational absorption bands is given. This allowed assignment of overtone and combination bands in the near-infrared region and an assessment of residual water contamination, which is low and can be expelled by evacuation. These ormosils have low intrinsic and extrinsic optical absorption in the visible spectral region and at useful wavelengths in the near-infrared.