Two explosive triazides of phosphorus(V), OP(N-3)(3) and SP(N-3)(3), have been prepared as neat substances and structurally characterized. Both compounds can be handled in gas, liquid, and solid states in submillimolar quantities. The melting points of OP(N-3)(3) and SP(N-3)(3) are +22 and -30 degrees C, respectively. The two triazides have been characterized by IR (Ar matrix and gas phase) and Raman (solid) spectroscopies. Their single-crystal structures were obtained by X-ray diffraction and found to be significantly distorted from the predicted ideal C-3 symmetry because of intermolecular interactions. The spectroscopic and structural properties are discussed in combination with density functional theory calculations.