The synthesis and structural properties (from X-ray diffraction or B3LYP/6-31G(d) calculations) of three energetic compounds derived from tris(chloromethyl)amine and of tris(chloromethyl)amine itself were investigated and compared to those of compounds with similar structures. The compounds have almost planar NC(3) units at their amine center, and the substituents bound to the CH(2) groups tend to be reactive towards further substitution. Multiple hyperconjugation was used to explain these observations.