Biodiesel has been considered to be the best substitute for diesel due to its unique qualities which contribute to environmental conservation. This work was undertaken to transesterification process and the production of biodiesel from waste cooking oil by electrolysis with a novel catalyst poly (AAc/AAm)/NaOH hydrogel. The catalyst was prepared by trapping sodium hydroxide in polyacrylic acid and acrylamide poly (AAc/AAm) to be used as a strong basic heterogeneous catalyst.The swelling of prepared hydrogel with different doses of cross-linker were examined. The Scanning electron microscopy (SEM) as well as the energy-dispersive X-ray spectroscopy (EDX) were employed to characterize the prepared catalyst. The degree of conversion of WCO to biodiesel expressed as fatty acid methyl esters (FAMEs) was determined via high performance thin layer chromatography (HPTLC), as well as the composition of FAMEs by gas chromatography mass spectrometry (GC/MS). Technical Details and Standards of biodiesel prepared from WCO were also characterized. Optimization of the electrolysis catalyzed process revealed that the optimum conditions employed for electrolysis process to produce the most promising results 92.8 % for biodiesel yield were oil: methanol molar ratio 1:35, dose of electrolyte salt (NaCl) 0.7g / 40 g oil, water dose used to dissolve the electrolyte salt 1.6 % related to oil volume and electrical potential required was 30 volt and catalyst dose 20% related to oil weight over a reaction duration of 60 minutes under ambient reaction conditions.