In the mol­ecular crystal of hexa­phenyl­hexa­phosphinane benzene solvate, C36H30P6·C6H6, representing the trigonal form of phospho­benzene as a solvate, the six-membered ring of P atoms adopts a chair conformation wherein the six phenyl groups are located in equatorial positions. The mol­ecules [mol­ecular symmetry \overline{3} (C3i)] are stacked infinitely along the c-axial direction.