Reported here is the first synthesis, X-ray crystal structure, and derivatization of benzotrifuran (BTFuran). Single crystal X-ray analysis of BTFuran shows a tight hexagonal packing stabilized by π-stacking interactions and C–H•••O contacts. α-Lithiation of BTFuran enables the preparation of reactive intermediates suitable for cross-coupling reactions, allowing access to representative BTFuran-containing π-conjugated systems.