Single-crystalline organic semiconductors exhibiting band transport have opened new possibilities for the utilization of efficient charge carrier conduction in organic electronic devices. The epitaxial growth of molecular materials is a promising route for the realization of well-crystallized organic semiconductor p-n junctions for optoelectronic applications enhanced by the improved charge carrier mobility. In this study, the formation of a high-quality crystalline interface upon "quasi-homoepitaxial" growth of bis(trifluoromethyl)dimethylrubrene (fmRub) on the single-crystal surface of rubrene was revealed by using out-of-plane and grazing-incidence X-ray diffraction techniques. Ultraviolet photoelectron spectroscopy results indicated abrupt electronic energy levels and the occurrence of band bending across this quasi-homoepitaxial interface. This study verifies that the minimization of the lattice mismatch enhances the crystalline qualities at the heterojunctions even for van der Waals molecular condensates, potentially opening an untested route for the realization of high-mobility organic semiconductor optoelectronics.