Supercritical processing technology has emerged as a readily available alternative for biofuel production since no catalyst is required and therefore fewer wastes are generated. In this paper, the production of a biofuel mixture by supercritical processing of refined palm oil and aqueous ethanol was carried out at temperatures 400 to 480 °C and a 12:1 ethanol to palm oil molar ratio, to assess the effect of temperature and residence time in the formation of a homogeneous phase, effluent appearance and increased water content derived from glycerol decomposition reactions. The results showed water was produced at temperatures higher than 400 °C, as expected from occurrence of glycerol decomposition, and that prolonged times resulted in gas and soot formation, indicating esters decomposition reactions. A model for an industrial plant was proposed and simulated in Aspen One software, and a LCA comparing the proposed process with previously reported simulation results was carried out in OpenLCA. The results indicated the proposed process had a similar environmental burden to the conventional base catalyzed process and considerably less than that for a different supercritical process.