Newly synthesized rare-earth metal alkyl complexes bearing a tripyrrolyl ligand act as excellent precatalysts for the cross-dehydrogenative coupling between various terminal alkynes and O/N-based monohydrosilanes of HSi(OEt)(3)/HSi(NMe2)(3), leading to the formation of a variety of alkoxysilylalkyne and aminosilylalkyne derivatives in good to high yields. The precatalysts LRE(CH2SiMe3)(thf)(2) (RE = Y(1a), Er(1b), Yb(1c), L = 2,5-[(2-C4H3N)CPh2](2)(C4H2NMe), thf = tetrahydrofuran) were easily prepared in high yields via the reactions of RE(CH2SiMe3)(3)(thf)(2) with the proligand H2L in a single step. Mechanistic studies reveal that treatment of 1 with phenylacetylene could generate the active catalytic species: dinuclear rare-earth metal alkynides (L(thf)(n)[RE(mu-C CPh)](2)L) (RE = Y(5a), n = 1; Yb(5c), n = 0), which could react with HSi(OEt)(3) to produce the coupling product 4aa and the dinuclear rare-earth metal hydrides (L (thf)[RE(mu-H)](2)L) (RE = Y(6a); Yb(6c)). By contrast, prior treatment of 1c with HSi(OEt)(3) proceeds via cleavage of the Si-O bond to produce the dinuclear ytterbium alkoxide (LYb(mu-OEt))(2) 7c, which is inert in the dehydrogenative coupling reaction. The results of the mechanistic studies are consistent with the observation that the reaction is greatly influenced by the addition sequence of precatalyst/alkynes/silanes.