The physical structure of an organic solid is strongly affected by the surface of the underlying substrate. Controlling this interface is an important issue to improve device performance in the organic electronics community. Here we report an approach that utilizes an organic heterointerface to improve the crystallinity and control the morphology of an organic thin film. Pentacene is used as an active layer above, and m-bis(triphenylsilyl) benzene is used as the bottom layer. Sequential evaporations of these materials result in extraordinary morphology with far fewer grain boundaries and myriad nanometre-sized pores. These peculiar structures are formed by difference in molecular interactions between the organic layers and the substrate surface. The pentacene film exhibits high mobility up to 6.3 cm(2)V(-1)s(-1), and the pore-rich structure improves the sensitivity of organic-transistor-based chemical sensors. Our approach opens a new way for the fabrication of nanostructured semiconducting layers towards high-performance organic electronics.X116049Nsciescopu