The chemistry of carbeniophosphines and phosphoniocarbenes, which have general structures derived formally from the three-component “carbene/phosphine/positive charge” association, is presented. These two complementary classes of carbon–phosphorus-based ligands, defined by the presence of an inverted cationic coordinating structure (C+∼P: vs. P+∼C:) have the common purpose of positioning a positive charge in the vicinity of the metal center. Through selected examples, the synthetic methods, coordination properties, and general reactivity of both cationic species is described. Particular emphasis is placed on the influence of the positive charge on the respective chemical behavior of the two classes of compound.