1,3-Enynes with the conjugated alkene and alkyne moieties are attractive building blocks in synthetic chemistry. However, neither 4,1-hydrophosphination nor dihydrophosphination of 1,3-enynes has been reported. In this paper,the divalent ytterbium and calcium amide complexes supported by silaimine-functionalized cyclopentadiene ligands (C5Me4-Si(L)=NR) were developed, which successfully catalyzed the efficient single and double hydrophosphination of 1,3-enynes with diarylphosphines. These two hydrophosphination reactions selectively produced homoallenyl phosphines and (E)-propenylene diphosphines, respectively. This work demonstrated the potential of hemilabile silaimine-Cp ligands in supporting the efficient and selective rare- and alkaline-earth catalysts.