Molecular structure and conformational properties of 2-fluoroanisole have been studied by gas electron diffraction and quantum chemical methods (HF/6-31G*, MP2/6-31G*, and B3LYP/6-31G*). All methods predict the existence of two minima on the potential to internal rotation around the C(sp(2))-O bond corresponding to planar and nonplanar forms, but they give rather different results on the geometry and the relative energy of the nonplanar conformation. The electron diffraction data were treated with two different procedures for obtaining the scattering intensities (scanner and densitometer) and two different procedures of structural analysis used in laboratories of Moscow and Tubingen. With all data sets and procedures used in analysis, geometrical parameters and conformational composition were found to be very close. The preferred conformation of 2-fluoroanisole is a planar anti form, 70 +/- 12%, whereas the minor conformation is a nonplanar form with the CH3 group rotated toward the F atom with phi(C=C-O-C) = 57(8)degrees. The structural parameters are compared with those obtained for related compounds. Stereochemical peculiarities in ortho derivatives of anisole, which result in the existence of a nonplanar conformer, are discussed in terms of a natural bond orbital (NBO) analysis.