The dynamical and conformational behaviour of a flexible tetrabenzocyclododecatetraene derivative exhibiting a columnar mesophase has been studied by a combination of deuteron solid state NMR spectroscopy and molecular dynamics (MD) simulations. As shown by two-dimensional (2D) exchange NMR, the mesophase is characterized by slow axial reorientations (∼10−3s) of single molecular units where the phenylene rings exhibit a well-defined quasi-fourfold potential, while the 2D spectra of the core methylene sites are sensitive to the molecular conformation and reorientation mechanism. Motional narrowing of one-dimensional (1D) spectra reveals additional fast librations due to the internal flexibility of the mesogenic moiety. The various reorientation pathways comprising interconversions and pseudo-rotations between different energetically stable conformations are elucidated on a microscopic level by molecular dynamics simulations. The mesophase dynamics is ascribed to a complex axial motion involving rotational jumps combined with a pseudo-rotation between two symmetry related sofa forms. This is confirmed quantitatively by comparing the experimental 2D NMR spectra of the core methylene sites and the simulations which are based on the molecular geometries obtained by MD simulations. The lineshapes of one- and two-dimensional spectra of magnetically aligned samples specific to the orientation behaviour of the sofa conformer are discussed.