In this study, a new method for the synthesis of heterometallic 3d–4f alkoxides by the direct reaction of metallic lanthanides (La, Pr, Nd, Gd) with MCl₂ (M = Mn, Ni, Co) in 2-methoxyethanol was developed. The method was applied to the synthesis of the heterometallic oxo-alkoxide clusters [Ln₄Mn₂(μ₆-O)(μ₃-OR)₈(HOR)_xCl₆] (Ln = La (1), Nd (2), Gd (3); x = 0, 2, 4); [Pr₄M₂(μ₆-O)(μ₃-OR)₈(HOR)_xCl₆] (M = Co (4), Ni (5); x = 2, 4); and [Ln₄Mn₂(μ₃-OH)₂(μ₃-OR)₄(μ-OR)₄(μ-Cl)₂(HOR)₄Cl₆] (Ln = La (11) and Pr (12)). Mechanistic investigation led to the isolation of the homo- and heterometallic intermediates [Pr(μ-OR)(μ-Cl)(HOR)Cl]_n (6), [Co₄(μ₃-OR)₄(HOR)₄Cl₄] (7), [Ni₄(μ₃-OR)₄(HOEt)₄Cl₄] (8), [Mn₄(μ₃-OR)₄(HOR)₂(HOEt)₂Cl₄] (9), and [Nd(HOR)₄Cl][CoCl₄] (10). In the presence of an external M(II) source at 1100 °C, 1–4 and 12 were selectively converted into binary metal oxide nanomaterials with trigonal or orthorhombic perovskite structures, i.e., LaMnO₃, GdMnO₃, NdMnO₃, Pr_0.9MnO₃, and PrCoO₃. Compound 5 decomposed into a mixture of homo- and heterometallic oxides. The method presented provides a valuable platform for the preparation of advanced heterometallic oxide materials with promising magnetic, luminescence, and/or catalytic applications.