Cryogenic transmission electron microscopy of polyoxometalate-protected gold nanoparticles reveals that the Preyssler ion, [NaP₅W₃₀O₁₁₀]^14–, lies “face down” with its C₅ axis perpendicular to the gold surface, while the Finke–Droege ion, [P₄W₃₀Zn₄(H₂O)₂O₁₁₂]^16–, is “tilted”, with its long axis close to 60° from the normal to the surface.