A novel synthesis producing neat 2-fluoroethyl azide (FCH2CH2N3) is described. A conformational analysis using microwave spectroscopy augmented by quantum chemical calculations at the CCSD(T)/cc-pVTZ, B3LYP/aug-cc-pVTZ, and B3LYP/cc-pVTZ levels of theory has been performed for this compound. The spectra of the ground vibrational state and two vibrationally excited states of one rotameric form were assigned. A large number of transitions was assigned, and very accurate values were obtained for the rotational and quartic centrifugal distortion constants. The identified conformer has synclinal orientations for the F-C-C-N and C-C-N-N-chains of atoms bringing the fluorine atom and the azido group into close proximity. It is concluded from consideration of absolute intensities that this conformer is indeed the preferred form of the molecule in accord with the theoretical calculations. The experimental and CCSD(T) rotational constants are in very good agreement, whereas much larger discrepancies were seen for the experimental and B3LYP quartic centrifugal distortion constants.