Organophosphines are versatile Lewis basic catalysts that have been confirmed as powerful tools in organic synthesis for the past two decades. The nucleophilic addition of organophosphines to electron-deficient species can be divided into two categories: phosphine-catalyzed and stoichiometric phosphine-mediated transformations. In this focus review, we summarize recent examples of phosphine-catalyzed addition and annulation reactions with allenoates and alkynoates. In addition, we discuss our recent efforts in the development of unusual phosphine-mediated alpha-addition reactions with enynedioates, enynoates, and oligoynoates and its application in novel functional fullerene derivatives as n-type materials in organic photovoltaics.