Lanthanide-organic complexes of the general type Ln[N(SiMe3)(2)](3) (Ln = La, Sm, Y, Lu) serve as effective precatalysts for the rapid, exoselective, and highly regioselective intramolecular hydroalkoxylation/cyclization of primary and secondary alkynyl alcohols to yield the corresponding exocyclic enol ethers. Conversions are highly selective with products distinctly different from those generally produced by conventional transition metal catalysts, and turnover frequencies as high as 52.8 h(-1) at 25 degrees C are observed. The rates of terminal alkynl alcohol hydroalkoxylation/cyclization are significantly more rapid than those of internal alkynyl alcohols, arguing that steric demands dominate the cyclization transition state. The hydroalkoxylation/cyclization of internal alkynyl alcohols affords excellent E-selectivity. The hydroalkoxylation/cyclization of the SiMe3-terminated internal alkynyl alcohols reveals interesting product profiles which include the desired exocyclic ether, a SiMe3-eliminated exocyclic ether, and the SiMe3-O-functionalized substrate. The rate law for alkynyl alcohol hydroalkoxylation/cyclization is first-order in [catalyst] and zero-order in [alkynyl alcohol], as observed in the intramolecular hydroamination/cyclization of aminoalkenes, aminoalkynes, and aminoallenes. An ROH/ROD kinetic isotope effect of 0.95(0.03) is observed for hydroalkoxylation/cyclization. These mechanistic data implicate turnover-limiting insertion of C-C unsaturation into the Ln-O bond, involving a highly organized transition state, with subsequent, rapid Ln-C protonolysis.