The traditional methods for the synthesis of phosphinate esters use phosphorus trichloride (PCl 3 ) as the phosphorous source, resulting in procedures that are often highly polluting and energy intensive. The search for an alternative approach that is both mild and environmentally friendly is a challenging, yet highly rewarding task in modern chemistry. Herein, we use an inorganic phosphorous-containing species, NaH 2 PO 2 , to serve as the source of phosphorous that participates directly in the nickel-catalyzed selective alkyne hydrophosphonylation reaction. The transformation was achieved in a multicomponent fashion and at room temperature, and most importantly, the H-phosphinate product generated is an advanced intermediate which can be readily converted into diverse phosphinate derivatives, including those bearing new P−C, P−S, P−N, P−Se, and P−O bonds, thus providing a complimentary method to classic phosphinate ester synthesis techniques.