The picture above shows an ampoule, in which phosphorus pentabromide and phosphorus heptabromide were made. This was made by adding bromine to phosphorus tribromide in such an amount that after formation of phosphorus pentabromide some bromine was left over. This excess bromine further reacts to form phosphorus heptabromide. Both compounds are present in the ampoule and it nicely demonstrates the color difference between the two bromides.

Phosphorus heptabromide, like phosphorus pentabromide, is only marginally stable. In the solid state, phosphorus pentabromide exists as a salt, being PBr₄⁺/Br₃^‒. In the gas phase it does not exist, on gentle heating it completely decomposes to PBr₃ and 2 Br₂. Its structure also shows that phosphorus does not have oxidation state +7 in phosphorus heptabromide, but oxidation state +5. It is the anion, which is special in this compound. The anion is a complex of bromide and bromine, very similar to the much better known tri-iodide ion I₃^‒. The ion Br₃^‒ only is stable when combined with large cationic species, such as PBr₄⁺ and Cs⁺. Another stable salt of Br₃^‒ is cesium tribromide.

When phosphorus heptabromide is added to water, copious amounts of bromine and hydrogen bromide are formed and phosphoric acid dissolves in the water.