Exergy and energy analyses of two biodiesel production processes that integrate solar energy as the main energy source were developed to determine the process with the higher efficiency from an energy and exergy approach. The biodiesel production processes were simulated in ASPEN PLUS^®, and the solar energy supply was studied in TRNSYS^®, using EXCEL^® simultaneously for the exergetic analysis. The solar thermal energy collection system can supply 81% of the energy required by the alkali process in the Flash separation equipment. For the supercritical process, solar thermal energy can supply 74.5% of the energy in the preheating and separation stages. The energy efficiency of the supercritical process is higher; nevertheless, the exergetic efficiency of the alkaline process is higher than the supercritical one. Solar collection systems contribute from 85% to 93% of the exergy destroyed by the global process for both cases. The alkaline biodiesel production process has the highest advantages when using solar energy as the main source of energy, compared to a process in supercritical conditions that presents greater irreversibilities and requires more infrastructure to collect the solar resource. However, using solar energy as the foremost energy source offers an alternative to fossil fuels, and it provides an environmental benefit concurrently with the use of biodiesel.