Highly oriented, domain-boundary-free organic thin films could find use in various high-performance organic materials and devices. However, even with state-of-the-art supramolecular chemistry, it is difficult to construct organic thin films with structural integrity in a size regime beyond the micrometer length scale. We show that a space-filling design, relying on the two-dimensional (2D) nested hexagonal packing of a particular type of triptycene, enables the formation of large-area molecular films with long-range 2D structural integrity up to the centimeter length scale by vacuum evaporation, spin-coating, and cooling from the isotropic liquid of the triptycene. X-ray diffraction analysis and microscopic observations reveal that triptycene molecules form a completely oriented 2D (hexagonal triptycene array) + 1D (layer stacking) structure, which is key for the long-range propagation of structural order.