The stability and some characteristic bonding features of a variety of ligand (L)-stabilized phosphinidene complexes derived from adduct formation with halides, and both anionic or neutral O-donor bases were explored. Furthermore, the main features of L → P pnictogen bonding in such adducts were studied not only by using geometric criteria such as L–P bond distances and pyramidalization or planarity at P but also by turning the spotlight on bond-strength-related (including atoms-in-molecules-derived) parameters, thermodynamic stability dependence with electronic characteristics of the free ligand, and dative-bonding participation. We propose the new relative positions of the charge concentration band descriptor, τVSCC, which, together with the sign and magnitude of ∇2ρ at the bond critical point, constitutes the required criteria to differentiate L–P linkages as van der Waals interactions, dative bonding, or mostly covalent bonds.