Direct alcohol fuel cells (DAFCs) are considered as reliable, clean and sustainable energy conversion technologies. However, most of them are reported using noble metal based electro-catalysts such as platinum (Pt), palladium (Pd) etc. which suffer from low cycling stability due to intermediate CO poisoning during the alcohol oxidation reaction (AOR). Herein, we report the solid-state synthesis of ruthenium nickel oxide (RuNiO3) modified nickel foam (RNO/NF) as a cost-effective perovskite based electrocatalyst for DAFC applications. The RNO/NF catalyst electrode exhibits a high current density of ∼711.15 mA cm−2 (0.4 M; ethanol), ∼475.05 mA cm−2 (0.3 M; methanol) and ∼579.1 mA cm−2 (0.3 M; ethylene glycol) at a potential of 0.8 V (vs. Hg|HgO). This superior performance of the RNO/NF electrode is ascribed to the presence of the Ni2+/3+ redox couple at the tetrahedral sites favouring the AOR with the oxidation of CO into CO2. The electrochemical active surface area of RNO/NF is estimated to be ∼175% greater than that of the bare NF which proves the activity of the electrode. The RNO/NF electrode displays high stability with a capacity retention of 88.79% (ethanol), 82.283% (methanol) and 95.54% (ethylene glycol) for 10 000 s which is higher than that of the commercial platinum-on-carbon (Pt/C) electro-catalyst, proving to be an ideal electrocatalyst for low-cost DAFC applications. © 2023 The Royal Society of Chemistry.