The reactions of laser-ablated late lanthanide atoms and methanol were studied using matrix isolation infrared spectroscopy and electronic structure calculations at the density functional theory level. Both terbium and lutetium atoms react with methanol spontaneously to form the CH(3)OTbH and CH(3)OLuH insertion products, which react further with another methanol molecule to give the Tb(OCH(3))(2) and Lu(OCH(3))(2) products as found previously for uranium. The reactions of Dy through Yb and methanol first produce Ln(CH(3)OH) complexes during sample annealing, which isomerize to the CH(3)OLnH insertion products on visible irradiation. The Ln-H stretching frequencies of the CH(3)OLnH molecules exhibit a unique trend from Tb to Lu, which is also reproduced by theoretical calculations at the B3LYP level of theory. Although the CH(3)LnOH molecules are predicted to be more stable than the O-H bond insertion products, formation of the C-O bond insertion isomers is kinetically prohibited as revealed by calculated potential energy surfaces.