Abstract：Various binary cluster anions consisted of carbon and nitrogen elements were produced on a self-built apparatus by laser ablation of K~3[Fe(CN)~6]. The mass distribution was recorded by a time-of- flight mass spectrometer. The mass-selected cluster ions dissociated in colliding with a nitrogen beam and the fragment ions were mass analyzed by the secondary mass spectrometer. Based on the analysis of the experimental results, two major structural styles of the binary cluster ions, linear chain and planar ring, were suggested. The cluster ions composed of single nitrogen atom is linear, and those consisted of more than two nitrogen atoms are mostly in ring structure. Most recorded cluster ions are highly conjugated and without dangling bond.