2,5-Di(1-naphthyl)-1-phenylphosphole (2) was prepared from phenylphosphine and dinaphthylbutadiyne in 70 % yield, and oxidized to its oxide 3. Treatment of 2 with a solution of potassium naphthalide results in selective formation of phospholide anion 4, which can be oxidized with iodine to afford biphosphole 5. The crystal structure of 5 exhibits an unusual s-trans conformation across the P–P bridge that is most stabilized by π–π stacking of the naphthyl substituents. Biphosphole 5 can be oxidized to its mono-oxidized 6 and dioxide 7. Generally, all phosphole oxidations lead to decreased pyramidalization of the P centres and, consequently, to significantly redshifted lowest-energy absorption maxima. Mono-oxidized biphosphole 6, which consists of an ordinary phosphole and an electron-deficient oxidized phosphole, features a unique low-energy optical transition (shoulder at 430 nm), which is tentatively assigned to a charge-transfer transition. The UV/Vis spectrum of dioxide 7 lacks this transition. At the same time, the emission maximum of 7 is bathochromically shifted by 80 nm relative to that of 5.