Ab initio and density functional theory methods are applied to investigate the molecular structure and conformational nature of tetrabromoformaldazine. The calculations including the effects of the electron correlation at the B3LYP and NIP2 levels with the basis set 6-311 + G(d) can reproduce the experimental geometrical parameters at the skew conformation. The N-N bond torsional angle phi calculated at the MP2/6-311 + G(d) level is found ro be closest to the observed angle. The scanning of the potential energy surface suggests that the anti-conformation is at a saddle point corresponding to the transition state.