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In this study, the transesterification process of 4 different vegetable oils (sunflower, rapeseed, olive oil and used frying oil) took place utilizing ethanol, in order to characterize the ethyl esters and their blends with diesel fuel obtained as fuels for internal combustion engines. All ethyl esters were synthesized using calcium ethoxide as a heterogeneous solid base catalyst. The ester preparation involved a two-step transesterification reaction, followed by purification. The effects of the mass ratio of catalyst to oil, the molar ratio of ethanol to oil, and the reaction temperature were studied on conversion of sunflower oil to optimize the reaction conditions in both stages. The rest of the vegetable oils were converted to ethyl esters under optimum reaction parameters. The optimal conditions for first stage transesterification were an ethanol/oil molar ratio of 12:1, catalyst amount (3.5%), and 80 °C temperature, whereas the maximum yield of ethyl esters reached 80.5%.