Homodinuclear multiple-bonded neutral Al compounds, aluminum analogues of alkenes, have been a notoriously difficult synthetic target over the past several decades. Herein, we report the isolation of a stable neutral compound featuring an Al=Al double bond stabilized by N-heterocyclic carbenes. X-ray crystallographic and spectroscopic analyses demonstrate that the dialuminum entity possesses trans-planar geometry and an Al Al bond length of 2.3943(16) angstrom, which is the shortest distance reported for a molecular dialuminum species. This new species reacts with ethylene and phenyl acetylene to give the [2+2] cycloaddition products. The structure and bonding were also investigated by detailed density functional theory calculations. These results clearly demonstrate the presence of an Al=Al double bond in this molecule.