New alkoxo-iron compounds can be synthesized easily by alcoholysis of [Fe2(OtBu)6] (1). Due to different bulkyness of the alcohols used, three different structure types are formed: [Fe 2(OR)6], [Fe5O(OR)13] and [Fe 9O3(OR)21]·ROH. We report synthesis and crystal structures of the compounds [Fe5OCl(OiPr) 12] (2), [Fe2(OtAmyl)6] (3), [Fe5O(OiPr)13] (4), [Fe5O(O iBu)13] (5), [Fe5O(OCH2CF 3)13] (6), [Fe9O3(O nPr)21] · nPrOH (7) and [Fe 5O(OnPr)13] (8). Cryslallographic Data: 2, tetragonal, P 4/n, a = 16.070(5) A, c = 9.831(5) A, V = 2539(2) A3, Z = 2, dc = 1.360 gcm-3, R 1 = 0.0636; 3, monoclinic, P 21/c, a = 10.591(5) A, b = 10.654(4) A, c = 16.740(7) A, β = 104.87(2)°, V = 1826(2) A3, Z = 2, dc = 1.154 gcm-3, R1 = 0.0756; 4, triclinic, P 1, a = 20.640(3) A, b = 21.383(3) A, c = 21.537(3) A, a = 82.37(1)°, β = 73.15(1)°, γ = 61.75(1)°, V = 8013(2) A3, Z = 6, dc = 1.322 gcm-3, R1 = 0.0412; 5, tetragonal, P 4cc, a = 13.612(5) A, c = 36.853(5) A, V = 6828(4) A3, Z = 4, dc = 1.079 gcm-3, R1 = 0.0609; 6, triclinic, P 1, a = 12.039(2) A, b = 12.673(3) A, c = 19.600(4) A, a = 93.60(1)°, β = 97.02(1)°, γ = 117.83(1)°, V = 2600(2) A3, Z = 2, dc = 2.022 gcm-3, R 1 = 0.0585; 7, triclinic, P 1, a = 12.989(3) A, b = 16.750(4) A, c = 21.644(5) A, α = 84.69(1)°, β = 86.20(1)°, γ = 77.68(1)°, V = 4576(2) A3, Z = 2, dc = 1.344 gcm-3, R1 = 0.0778; 8, triclinic, P 1, a = 12.597(5) A, b = 12.764(5) A, c = 16.727(7) A, α = 91.94(1)°, β = 95.61(1)°, γ = 93.24(2)°, V = 2670(2) A3, Z = 2, dc = 1.323 gcm-3, R 1 = 0.0594.