Synthesis of a new class of heteroleptic samarium aryloxide complexes has been achieved by the use of homoleptic samarium(II) bis(aryloxide) Sm(OAr)(2)(THF)(3) (1, Ar = C(6)H(2)Bu(2)(t)-2,6-Me-4) as a starting material, which is easily obtained by reaction of Sm(N(SiMe(3))(2))(2)(THF)(2) with 2 equiv of ArOH in THF. 1 reacts with 1 equiv of SmI2 in THF to give Sm(II) mixed aryloxide/iodide [(ArO)Sm(mu-I)(THF)(3)](2) (2), which adopts a dimeric structure via very weak Sm ... I (3.534(2) Angstrom) interactions. Reaction of 2 with C(5)Me(5)K in THF/HMPA affords the corresponding Sm(II) aryloxide/cyclopentadienide (C(5)Me(5))Sm(OAr)(HMPA)(2) (3). Oxidation of 1 with 0.5 equiv of I-2 in THF gives monomeric samarium(III) aryloxide/iodide (ArO)(2)SmI(THF)(2) (4), while the similar reaction of 1 with ClCH2-CH2Cl or (t)BuCl in THF affords dimeric samarium(III) aryloxide/chloride [(ArO)(2)Sm(mu-Cl)(THF)](2) (5). Crystal data for 1 : monoclinic, space group P2(1), a = 9.903(3) Angstrom, b = 16.718(5) Angstrom, c = 13.267(2) Angstrom, beta = 95.17(2)degrees, V = 2187(2) Angstrom(3), Z = 2, D-c = 1.223 g cm(-3), R = 0.0634. Crystal data for 2 . 2THF : monoclinic, space group P2(1)/a, a = 18.330(6) Angstrom, b = 14.320(4) Angstrom, c = 13.949(3) Angstrom, beta = 103.16(2)degrees, V = 3563(2) Angstrom(3), Z = 2, D-c = 1.46 g cm(-3), R = 0.0606. Crystal data for 3 : triclinic, space group P (1) over bar, a = 10.528(1) Angstrom, b = 12.335(2) Angstrom, c = 19.260(2) Angstrom, alpha = 101.33(1)degrees, beta = 95.230(9)degrees, gamma = 108.54(1)degrees, V = 2293.1(5) Angstrom(3), Z = 2, D-c = 1.25 g cm(-3), R = 0.0358. Crystal data for 4 : monoclinic, space group C2/c, a = 17.191(7) Angstrom, b = 10.737(6) Angstrom, c = 21.773(7) Angstrom, beta = 98.80(3)degrees, V = 3971(3) Angstrom(3), Z = 4, D-c = 1.44 g cm(-3), R = 0.0467. Crystal data for 5 : monoclinic, space group P2(1)/n, a = 13.750(3) Angstrom, b = 17.231(3) Angstrom, c = 14.973(6) Angstrom, beta = 95.81(2)degrees, V = 3529(2) Angstrom(3), Z = 2, D-c = 1.31 g cm(-3), R = 0.0557.