The synthesis, structural characterization, electrochemistry and luminescence properties of a series of new yttrium and europium(+3) alkoxides bearing thiophene moieties are presented. The yttrium compounds were obtained by the reaction between Y[N(SiMe3)2]3and the tertiary alcohols HO–C(C16H13S) (2), HO–C(C17H15S) (3), HO–C(C14H11S2) (4) and HO–C(C16H13S) (5) in thf or in a mixture of toluene and pyridine. The X-ray crystal diffraction measurements show a five-coordinated yttrium atom in distorted trigonal-bipyramidal geometry. The metal centres are surrounded by threemethoxido ligands in equatorial positions and two tetrahydrofuran [for {Y[OC(C16H13S)]3(thf)2}·toluene (8), {Y[OC(C17H15S)]3(thf)2}·toluene (10) and {Y[OC(C14H11S2)]3(thf)2}·1/2 toluene (12)] or two pyridine [for {Y[OC(C16H13S)]3(py)2}·toluene (9) and {Y[OC(C17H15S)]3(py)2}·toluene (11)] molecules in axial positions. The compounds Y[OC(C14H11S2)]3(py)2(13) and Y[OC(C16H13S)]3(py)2(14) were identified by NMR spectroscopy. In addition, a novel europium(+3) alkoxide {Eu[OC(C4H3S)3]3(thf)3}·thf (15) was synthesized by the reaction between Eu[N(SiMe3)2]3and the tertiary alcohol HO–C(C4H3S)3(1) in thf. The molecular structure of this compound reveals an approximately octahedral coordination sphere around the europium(+3) metal centre with three methoxido ligands and three facially arranged tetrahydrofuran molecules. The cyclic voltammograms of the yttrium alkoxides indicate that the electrochemical properties are essentially dominated by the organic ligands. The electrochemical properties of {Eu[OC(C4H3S)3]3(thf)3}·thf (15) are dominated by the oxidation of the thienyl moieties and in addition a reduction wave due to the reduction of Eu3+to Eu2+is visible. In comparison to the carbinols, the oxidation peak potentials of the thienyl units for the yttrium and europium(3+) alkoxides are marginally shifted towards higher values. The emission spectra of the carbinols and their derived yttrium compounds display broad bands attributed to the π*→π transitions of the aromatic ligands. Luminescence studies performed on compound15reveal the typical f–f transitions of the Eu3+ions and suggest that an energy transfer from the ligand to the metal atom operates.