A highly conductive metallic gas that is quantum mechanically confined at a solid-state interface is an ideal platform to explore nontrivial electronic states that are otherwise inaccessible in bulk materials. Although two-dimensional electron gas (2DEG) has been realized in conventional semiconductor interfaces, examples of two-dimensional hole gas (2DHG), which is the counter analogue of 2DEG, are still limited. Here, we report the observation of a 2DHG in solution-processed organic semiconductors in conjunction with an electric double-layer using ionic liquids. A molecularly flat single crystal of high mobility organic semiconductors serves as a defect-free interface that facilitates two-dimensional confinement of high-density holes. Remarkably low sheet resistance of 6 kΩ and high hole gas density of 1014 cm14 result in a metal-insulator transition at ambient pressure. The measured degenerated holes in the organic semiconductors provide a broad opportunity to tailor low-dimensional electronic states using molecularly engineered heterointerfaces.