The electrocatalytic properties of Ru complexes are of great technological interest given their potential application in reactions such water splitting and CO₂ reduction. In this work, a novel terpyridine-based Ru(II) complex, [RuCl(trpy)(acpy)], trpy = 2,2′:6′,2′′-terpyridine, acpy⁻ = 2-pyridylacetate was synthesized and its spectroscopic, electrochemical and catalytic properties were explored in detail. In dry acetonitrile, the complex exhibits two reduction peaks at −1.95 V and −2.20 V vs. Fc/Fc⁺, attributed to consecutive 1 e⁻ reduction. Under CO₂ atmosphere, a catalytic wave is observed (E_onset = 2.1 V vs. Fc/Fc⁺), with CO as the main reduction product. Bulk electrolysis reveals a turnover number (TON) of 12 (k_obs = 1.5 s⁻¹). In the presence of 1% water, an improvement in the catalytic activity is observed (TON_CO = 21 and k_obs = 2.0 s⁻¹) and, additionally, formate was also detected (TON_HCOO = 7). Spectroelectrochemical experiments allowed the identification of a metallocarboxylate (Ru–COO⁻) intermediate under anhydrous conditions, while in water, the partial labilization of the acpy⁻ ligand was observed in the course of the catalytic cycle. The experimental data was combined with DFT calculations, allowing the proposal of a catalytic cycle. The results establish important relationships between selectivity, ligand structure and reaction conditions.