AbstractSamples of paracyanogen were prepared by the pyrolysis of silver cyanide, the photolysis of cyanogen, and by sputtering a carbon electrode in a nitrogen plasma. This work was undertaken to establish whether these materials are alike and to derive structural information on the basis of FT‐IR, 13C‐MAS—NMR, and through temperature‐programmed thermal decomposition. Paracyanogen derived from the above sources is indeed alike spectrally and thermally. Paracyanogen is a polymer that incorporates carbon, mostly sp2, and nitrogen in a disordered structure. Cyanogen is the main volatile component released in the thermal decomposition of paracyanogen. The cyanogen released was identified by FT‐IR and MS. The rate of release reaches a maximum at ca. 700°C. Paracyanogen is not an appropriate carbon nitride precursor because of its limited thermal stability. © 1993 John Wiley & Sons, Inc.