Electron microscopy methods have been used to investigate the structure and morphology of a hexagonal columnar mesophase, formed by novel amphiphilic and dendrimeric liquid crystals. Alignment of the columns is examined by a surface condition that is suitable for the molecular architecture. For all the materials investigated, columns aligned perpendicular to an evaporated carbon surface. In the case of asymmetric amphiphilic compounds, planar alignment of asymmetric compounds was induced by a water surface. However, planar alignment on water was not possible for a symmetric dendrimer. Based on analysis of electron diffraction and images, the dimension and the stiffness of columnar assemblies is found to depend on molecular architecture.