Difluoreno[4,3-b:3′,4′-d]furan (DFFu) was prepared via a short, scalable, multi-step synthesis, and characterized by crystallography, spectroscopic measurements, and theoretical calculations. Even though the results revealed an open-shell singlet diradical character, DFFu is stable under ambient conditions. The radical cationic and dianionic species of DFFu were also synthesized and characterized.