We investigated transport properties of organic heterointerfaces formed by single-crystals of two organic donor-acceptor molecules, tetramethyltetraselenafulvalene and 7,7,8,8-tetracyanoquinodimethane (TCNQ). Whereas the individual crystals have unmeasurably high resistance, the interface exhibits a resistivity of few tens of megohm with a temperature dependence characteristic of a small gap semiconductor. We analyze the transport properties based on a simple band diagram that naturally accounts for our observations in terms of charge transfer between two crystals. Together with the recently discovered tetrathiafulvalene–TCNQ interfaces, these results indicate that single-crystal organic heterostructures create functional electronic systems with properties relevant to both fundamental and applied fields.