The molecular structure of (fluoromethyl)dimethylamine, CH2FN(CH3)(2), has been determined by gas electron diffraction (GED), ab initio (HF/3-21G(*) (polarization functions only at nitrogen), and MP2/6-311G(2d,p)), and local density functional (VWN/TZVP) calculations. According to the GED analysis only the anti conformer (C-F bond antiperiplanar to the nitrogen lone pair) is present. The following skeletal geometric parameters (r(a) distances and angle(a) angles with 3 sigma error limits) were obtained : N-CH2F = 1.408(13) Angstrom, N-CH3 = 1.466(9) Angstrom, C-F = 1.410(5) Angstrom, (C-N-C)(mean) = 111.6(10)degrees, and N-C-F = 115.9(24)degrees. The results are discussed on the basis of the generalized anomeric effect. The theoretical calculations predict a second stable conformer with synclinal orientation of the C-F bond and 4.5-5.3 kcal mol(-1) higher in energy.