Described herein is the enantioselective construction of oxygen‐containing 5‐6‐5 tricyclic heterocycles by an organocatalyzed asymmetric 4+2 cycloaddition of vinylidene ortho‐quinone methides and benzofurans. According to this methodology, a series of oxygen‐containing 5‐6‐5 tricyclic heterocycles with various functional groups were synthesized in excellent enantio‐ and diastereoselectivities (>99 % ee, >20:1 d.r.). Furthermore, the deuterium‐labeling experiments and high‐resolution mass spectroscopy demonstrated that a vinylidene ortho‐quinone methide intermediate was involved and possibly resulted from a prototropic rearrangement of 2‐ethynylphenol. Remarkably, a catalyst loading as low as 0.1 mol %, and a gram‐scale synthesis were achieved for this transformation. Triple play: The enantioselective construction of oxygen‐containing 5‐6‐5 tricyclic heterocycles by a thiourea‐catalyzed asymmetric 4+2 cycloaddition of vinylidene ortho‐quinone methides (VQMs) and benzofurans is reported. A series of oxygen‐containing 5‐6‐5 tricyclic heterocycles having various functional groups were synthesized with excellent enantio‐ and diastereoselectivities.