Hexaphenyldisiloxane-benzene (1/2), C_36- H₃₀OSi₂.2C₆H₆, M_r- = 691.0, hexagonal, R3, α = 11.196(4), c = 26.515(15) Å, V = 2878 (2) ų, Z = 3, D_x = 1.20 g cm^-3, Mo Kα, λ = 0.71069 Å, μ = 1.228 cm^-1, F(000) = 1098, T = 150 K, R = 0.056 for 856 unique observed reflections. Hexaphenyldisiloxane-piperidine (1/2), C₃₆H₃₀OSi₂.2C₅H₁₁N, M_r = 705.1, hexagonal, R3, α = 11.197 (3), c = 27.670 (12) Å, V= 3004 (2) ų, Z = 3, D_x = 1.17 g cm^-1, Mo Kα, λ = 0.71069 Å, μ = 1.198 cm^-1, F(000) = 1134, T = 150 K, R = 0.074 for 781 unique observed reflections. The molecules lie in special positions on the crystallographic threefold axes. A cavity-type packing of bis(triphenylsilane) oxide (BTPSO) molecules occurs. The guest molecules occupy cavities between the host molecules. In the clathrate with piperidine (BTPSO/PP) disorder of the guest was observed. A crystal-packing-energy analysis was performed to establish the orientation of the piperidine molecule.