The conformations of allyl isocyanate (CH2=CHCH2N=C=O) were explored in the gas phase by combining theoretical calculations and Fourier transform microwave spectroscopy, including the chirped pulse and Balle-Flygare types. Three conformers (I, II, and III) were predicted using D3(BJ) dispersion-corrected B3LYP and MP2 methods; however, the lowest energy conformer (conf. I) was absent at the standard B3LYP level. The observed microwave spectra are consistent with the presence of both conf. I and III in the supersonic jet, and surprisingly, this is the first report of the global minimum conf. I both experimentally and theoretically. Rotational transitions from the parent species of both conformers as well as their minor isotopologues (13C, 15N, and 18O) in natural abundance were assigned allowing experimental geometries to be derived. For conf. I, in addition to the typical splitting pattern due to the 14N quadrupole nucleus, the transitions show a tunneling splitting which arises from the interconversion motion between its two mirror images. The experimental observation of conf. I and the absence of conf. II in the jet are rationalized using quantum-chemical calculations to explore the importance of electron correlation and in particular, demonstrate the necessity of including dispersion effects in density functional theory calculations even for seemingly small molecules.