Abstract: Disclosed are criteria for a lattice matched, multilayer, organic crystal heterostructure. Current organic devices (e.g., photovoltaics, light emitting diodes, or transistors) rely on amorphous material despite superior charge transport properties of crystalline organic semiconductors. Achieving a fully crystalline device architecture requires growth of a molecular crystal atop a different one, or heteroepitaxy, and is particularly relevant in organic semiconductor devices that demand multiple layers of different molecules. This challenge is complicated when attempting to stack highly ordered layers needed for crystalline devices because strategies are needed to ensure that each layer grows crystalline. It is shown herein that lattice matching alone is not sufficient for successful organic heteroepitaxy deposited via physical vapor deposition.