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Herein, we report on the homogeneous photocatalytic evolution of hydrogen by using as reductive catalysts the prismatic symmetric tris -dithiolene complexes of the tungsten, namely [W{S 2 C 2 (Ph) 2 } 3 ] (1) and its monoanion [W{S 2 C 2 (Ph) 2 } 3 ](TBA) (2). Complex 2 is fully characterized by elemental analysis, ESI-MS, IR, UV-Vis and fluorescence spectrophotometry as well as cyclic voltammetry. The photocatalytic system consists of [ReBr(CO) 3 (bpy)] as a photosensitizer, triethanolamine as a sacrificial electron donor and acetic acid as the proton source. Although the activity of the photocatalytic system is rather small (TON=18), it indicates that the homoleptic tris dithiolene complexes can act as proton reductive catalysts with their monoanion form to be more active in accordance with the findings for the bis -dithiolene complexes.