We report on XANES-investigations at the nitrogen and carbon K-edge of Si-C-N containing solid phases prepared by the reaction of silicon tetrachloride with bis(trimethylsilyl)carbodiimide and annealing the reaction product at temperatures between room temperature (RT) and 1600 °C. From the spectra it is possible to evidence the evolution of four phase regions and their different structural increments. We can relate the observed changes of atomic excitations to chemical and structural effects. By that means proposed structural models for the different phases are testified.