In this paper a novel synthetic route, being a paradigm of the “direct synthesis” approach, is proposed for the preparation of heterometallic Mn/V compounds by a one-pot reaction. Two synthesized complexes, (NH 4 ) 2 [Mn 2 (HGly)(H 2 O) 10 ][V 10 O 28 ]·(HGly)·2H 2 O (1) and (NH 4 ) 2 [Mn(β-HAla)(H 2 O) 5 ] 2 [V 10 O 28 ]·2H 2 O (2) (HGly=glycine, β-HAla=β-alanine) have been fully characterized by elemental analysis, single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, FTIR and EPR spectroscopy. Thermal degradation of these compounds lead to the formation of porous, solid mixed oxides V 2 O 5 /MnV 2 O 6 in a ratio of 3:2, which were analyzed by X-ray phase analysis and scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX). Additionally the ability of 1 and 2 to act as oxygen evolving water oxidation catalysts under visible light-driven conditions have been studied in a Clark type cell and by ex situ EPR spectroscopy.