Two-dimensional layered covalent organic frameworks (2D COFs) organize g-electron systems into ordered structures ideal for exciton and charge transport and exhibit permanent porosity available for subsequent fiinctionalization. A 2D COF with the largest pores reported to date was synthesized by condensing 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 4,4'-diphenylbutadiynebis(boronic acid) (DPB). The COF was prepared as both a high surface area microcrystalline powder as well as a vertically oriented thin film on a transparent single-layer graphene/fused silica substrate. Complementary molecular dynamics and density functional theory calculations provide insight into the interlayer spacing of the COF and suggest that adjacent layers are horizontally offset by 1.7-1.8 angstrom, in contrast to the eclipsed AA stacking typically proposed for these materials.