Using a specimen cyanided at 780°C for 15 hrs and having a comparatively thick outer layer, the qualities of the layer were mainly investigated. It was confirmed that the outer layer consists of a compound layer and a composite layer contained compound and solid solution. It was clarified that the partial extinction in the cementite diffraction patterns is due to existence of martensite, and definition of the term “outer layer” was given. Also, the carbo-nitriding diagram of this case was decided, and the correlation of the diagram with the thermal changes of the case was explained.