The observations reported herein investigate the methanol assisted water oxidation using a noble metal free LSCO perovskite in alkaline medium at near thermodynamic potential. There are several experimental evidences that points to the fact that rate of OER enhances both in alkaline and the neutral medium in presence of methanol. Clearly, this confirms that methanol assists the water oxidation process. Quantitatively, the moles of evolved oxygen are 460 nanomoles/ml in KOH and 840 nanomoles/ml in KOH + methanol. Similar enhancement is also noticed in the electro-oxidation current. RRDE experiments provide a very important insight into the assisted water oxidation as well as the catalyst's behaviour. RRDE demonstrate that the onset of oxygen reduction decreases by 70 mV on presence of methanol, another evidence of methanol assisted water oxidation. Interestingly, ring current demonstrate that LSCO catalysts exchanges the lattice oxygen with the aqueous electrolyte which opens a new dimension on the applicability of RRDE experimentation. A detailed study on the open circuit potential (OCP) study explains the adsorption behaviour of KOH and methanol. By the OCP study it is established that the main reason behind the elevated OER phenomenon is the enhanced concentration of hydroxyls due to methanol chemisorption; a kinetic effect. orcid.org/0000-0002-5217-9941; Email: ssharma@iitgn.ac.in