<p> [5.5.5.5]hexaene is a [12]annulene ring with a symmetrically bound carbon atom in its center. This is the smallest hydrocarbon with a hyperbolic paraboloid shape. [5.5.5.5]hexaene and related hydrocarbons are important building blocks in organic and materials chemistry. For example, pentagraphene—a puckered 2D allotrope of carbon—is comprised of similar repeating subunits. Here, we investigate the thermochemical and kinetic properties of [5.5.5.5]hexaene at the CCSD(T) level by means of the G4 thermochemical protocol. We find that this system is energetically stable relative to its isomeric forms. For example, isomers containing a phenyl ring with one or more acetylenic side chains are higher in energy by ∆_H298 = 17.5–51.4 kJ mol⁻¹. [5.5.5.5]hexaene can undergo skeletal inversion via a completely planar transition structure; however, the activation energy for this process is ∆H‡_H298 = 249.2 kJ mol⁻¹ at the G4 level. This demonstrates the high configurational stability of [5.5.5.5]hexaene towards skeletal inversion. [5.5.5.5]hexaene can also undergo a π-bond shift reaction which proceeds via a relatively low-lying transition structure with an activation energy of ∆H‡_H298 = 67.6 kJ mol⁻¹. Therefore, this process is expected to proceed rapidly at room temperature.</p>