Variable temperature (−55 to −131 °C) studies of the infrared spectra (4000–50 cm −1) of 2-fluoroethylamine, FCH 2CH 2NH 2 dissolved in liquid xenon and the far infrared in liquid krypton have been carried out. From these data all five possible conformers have been identified and their relative stabilities obtained. The enthalpy differences have been determined among the most stable Gg′ conformer and the second stable conformer, Gt, to be 62 ± 8 cm −1 (0.74 ± 0.10 kJ/mol), the third stable conformer, Tg, to be 262 ± 26 cm −1 (3.14 ± 0.3 kJ/mol), the fourth most stable conformer, Tt, to be 289 ± 45 cm −1 (3.46 ± 0.5 kJ/mol) and the fifth most stable conformer, Gg to be 520 ± 50 cm −1 (6.24 ± 0.6 kJ/mol). The percentage of each conformer at ambient temperature is estimated to be with Gg′ (42 ± 4%), Gt (32 ± 1%), Tg (13 ± 1%), Tt (5 ± 1%) and Gg (3 ± 1%). The first indicator is the NCCF dihedral angle (G = gauche or T = trans) and the second one (g = gauche or t = trans) is the relative position of the lone pair of electrons on the nitrogen atom with respect to the fluorine atom. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug-cc-pVTZ for both MP2(full) and density functional theory calculations by the B3LYP method. By utilizing previously reported microwave rotational constants along with ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r 0 parameters have been obtained for the two most stable conformers. The determined heavy atom structural parameters for the Gg′[Gt] conformer are: the distances (Å) C 1–C 2 = 1.509(3) [1.516(3)], C 2–N 3 = 1.466(3)[1.461(3)], C 1–F 4 = 1.400(3)[1.398(3)] and angles in degrees ∠N 3C 2C 1 = 109.8(5) [115.5(5)], ∠F 4C 1C 2 = 109.2(5)[109.3(5)], ∠H 10N 3H 9 = 107.1(5) [107.1(5)](°) and τF 4C 1C 2N 3 = 65.3(5) [60.9(5)]. Vibrational assignments have been provided for most of the observed bands which have been supported by MP2(full)/6-31G(d) ab initio calculations to predict harmonic force fields, frequencies, infrared intensities, Raman activities and depolarization ratios for all five conformers. The results are discussed and compared to the corresponding properties of some similar molecules.