A series of luminescent, neutral pentacoordinate dithieno[3,2‐b:2’,3’‐d]phosphole compounds was synthesized by [4+1] cycloaddition of o‐quinones with the corresponding trivalent phospholes. The electronic and geometrical modification of the π‐conjugated scaffold implemented here impacts the aggregation behavior of the species in solution. It proved successful in generating species with improved Lewis acidity of the phosphorus center that was then leveraged for small‐molecule activation. Hydride abstraction from an external substrate involving the hypervalent species is followed by an intriguing P‐mediated umpolung from the hydride to a proton and supports the catalytic potential of this class of main‐group Lewis acids for organic chemistry. This study is a comprehensive investigation into various methods, including electronic, chemical, geometric modifications (and sometimes combinations of these approaches) to systematically improve the Lewis acidity of neutral and stable main‐group Lewis acids with practical value for a range of chemical transformations.