Gallaphosphene L(Cl)GaPGaL 1 (L = HC[C(Me)N(2,6-i-Pr-2-C6H3)](2)) reacts at ambient temperature with a series of polar X-H bonds, i.e. ammonia, primary amines, water, phenol, thiophenol, and selenophenol, selectively with 1,2 addition at the polar Ga-P double bond. The gallium atom serves as electrophile and the phosphorous atom is protonated in all reactions. The resulting complexes L(Cl)GaP(H)Ga(X)L (X = NH2 2, NHi-Pr 3, NHPh 4, OH 5, OXyl 6, SPh 7, SePh 8) were characterized by IR and heteronuclear (H-1, C-13 {H-1}, P-31{H-1}) NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction.