The gas-phase structures of N,N-dimethylvinylamine, (CH3)(2)NC(H)=CH2 (1), and perfluoro-N,N-dimethylvinylamine, (CF3)(2)NC(F)=CF2 (2), were determined by gas electron diffraction and quantum chemical methods (B3LYP and MP2 with 6-31G* basis sets). The configuration around nitrogen is slightly pyramidal in both compounds, with the sum of the nitrogen bond angles 351.2(12)degrees and 354 8(6)degrees in 1 and 2, respectively. In the parent compound 1, the (CH3)(2)N group lies nearly in the plane of the vinyl group, and the nitrogen lone pair (lp) is almost perpendicular to this plane (Phi (C=C-N-lp) = 98(6)degrees). In the perfluorinated species 2, however, the (CF3)2N group is oriented perpendicular to the vinyl plane, and the lone pair is parallel to the C=C bond (Phi (C=C-N-lp) = 2(5)degrees). A natural bond orbital analysis provides a qualitative explanation for this conformational change upon fluorination. The sterically unfavorable in-plane orientation of the dimethylamino group in 1 is stabilized by conjugation between the nitrogen lone pair and the C=C pi -bond. The anomeric effect between the lone pair and the C-alpha-F sigma -bond in addition to steric effects favors the perpendicular orientation of the (CF3)(2)N group in 2. Both quantum chemical methods reproduce the experimental structures satisfactorily.