In this contribution, a review of the use of solid state NMR in the field of Si-based Polymer Derived Ceramics is presented. This synthetic approach allows to prepare a large variety of precursors leading to a wide range of ceramics, both in terms of composition and microstructure: multinuclear solid state NMR is obviously a pertinent spectroscopic tool of investigation since its versatility provides a detailed description of the structure of the polymeric precursors and their pyrolysis products. In a first introductory section, the relevant nuclei that can be probed in such systems are presented with their advantages and drawbacks, as well as the main NMR sequences that have been used to obtain as much structural information as possible in terms of local environments and connectivities. All along this article, examples are then given to illustrate which solid state NMR techniques are currently available to characterise the structure of a large variety of PDCs screening Si-C, Si-C-O, Si-/Ti/B/Al-C-O, Si-C-N, and Si-B/Al/Ti/Zr-N systems.