Department of Physical Chemisty, Indian Association for the Cultivation of Science, Jadavpur, Calcutta·32 Manuscript received 25 May 1974; revised 18 September 1974; accepted 18 November 1974 When ordinary electrolysis is carried out at an applied voltage much higher than the decomposition potential, following an incubation period a spontaneous transition to a new type of electrolysis (called galvanoluminescence) accompanied by appearance of lumninescence at an electrode preferentially at the cathode, occurs. The chemical effects of cathode glow process have been investigated. The chemical results of cathode glow remarkably differ from those by conventional electrolysis in that the yield is in excess of the Faraday law value and that the gas liberated at the glowing cathode is a liberal mixture of hydrogen and oxygen. Further depending upon the nature of electrolyte other unconventional products may be obtained. Effects of variables like voltage, current, area and intensity of luminosity and nature of glow condition on the degree of these non-Faradaic features have been studied. A critical analysis of the chemical results produced by cathode glow in a variety of aqueous electrolytes has been made. The results have been shown to be partly Faradaic and partly non-Faradaic. An interpretation based on energy transfer and charge transfer mechanisms has been offered.