The structure of iron pentacarbonyl, Fe(CO)(5), was reinvestigated by gas-phase electron diffraction using an experimental rotational constant available from the literature as a constraint on the structural parameters. The study utilized a B3LYP/6-311+G(d) ab initio quadratic force field, scaled to fit observed infrared wavenumbers, from which were calculated corrections for the effects of vibrational averaging on distances and certain other quantities useful for the structural analysis. The results confirm that the equatorial Fe-C bonds are longer than the axial ones, an important difference with the structure in the crystal where the equatorial Fe-C bonds are the shorter. Some distance (r(g)/Angstrom) and vibrational amplitude (l(alpha)/Angstrom) parameter values with estimated 2 sigma uncertainties based on assumption of D-3h symmetry are (r(Fe-C)) = 1.829(2), r(Fe-C)(eq) - r(Fe-C)(ax) = 0.032(20), (r(C=O)) = 1.146(2), r(C=O)(eq) - r(C=O)(ax) = 0.006(27), r(Fe-C)(ax) = 1.810(16), r(Fe-C)(eq) = 1.842(11), r(C=O)(ax) = 1.142(23), r(C=0)(eq) = 1.149(16), l(Fe-C)(ax) = l(Fe-C)(eq) = 0.047(5), and l(C=O)(ax) = l(C=O)(eq) 0.036(3).