Zirconium complexes stabilized by amine-bridged bis(phenolato) ligands showed good activity and chemo-selectivity in catalyzing intermolecular hydrophosphination of C–C multiple bonds with primary phosphines under mild conditions. A broad range of alkenes and alkynes underwent a mono-addition reaction with phenylphosphine, which generated secondary phosphines in 39–99% yields and >7 : 1 selectivity (over double hydrophosphination).