A series of neutral pentacoordinate dithieno[3,2-b:2′,3′-d]phosphole compounds were synthesized by [4 + 1] cycloaddition with o-quinones. Counter to the expected trigonal bipyramidal geometry, the luminescent hypervalent dithienophospholes exhibit square pyramidal geometry with inherently Lewis acidic phosphorus center that is stabilized via supramolecular π-stacking interactions in the solid state and in solution. Due to their Lewis-acid character, the compounds react with nucleophiles, suggesting their potential as mediator in organic transformations. The new species thus present an intriguing structural plaform for the design of neutral P(V) Lewis acids with useful reactivities.