A new global minimum for [12]annulene has been computationally located. This mono-trans minimum5 (CCCCCT) is computed to be 1.5 kcal/mol more stable (CCSD(T)/cc-pVDZ//BHHLYP/6-311+G**)than the known tri-trans isomer 1 (CTCTCT) and 2.4 kcal/mol lower than the di-trans isomer 4 (CCTCCT),for which there is indirect evidence. The barriers for several rearrangements of 5 were all computed tobe above 15 kcal/mol, indicating that direct experimental characterization of 5 should be possible. Thecomputed barriers for the dynamic processes (including conformational automerization) coupled withcomputed 1H NMR shift values should aid in the future characterization of this [12]annulene isomer.