Investigations of two-photon polymerization (TPP) with sub-100 nm in the structuring resolution are presented by using photosensitive sol-gel material. The high photosensitivity of this material allows for TPP using a large variety in laser pulse durations covering a range between sub-10 fs and 140 fs. In this study, the authors demonstrate TPP structuring to obtain sub-100 nm in resolution by different approaches, namely, by adding a cross-linker to the material and polymerization with sub-10 fs short pulses. Additionally, a simulation and model based characterization method for periodic sub-100 nm structures was implemented and applied in an experimental white light interference Fourier-Scatterometry setup.