In this work, the effect of using Sodium Hydroxide (NaOH) as catalyst on the synthesis of Biodiesel from castor oil and ethanol under subcritical and supercritical conditions (200 °C to 350 °C at endogenous pressure) is studied. The influence of the operating variables: temperature, reaction time, ethanol:oil molar ratio and catalyst concentration (when used) on the reaction conversion was analyzed using designs of experiments along with the surface response methodology for both the catalytic and non-catalytic processes. It was verified that using 0.1 % wt of NaOH, for the catalytic process, which is a lowest amount than the required to neutralize the oil, it is possible to obtain high conversions. The maximum conversion reached was 98.9 % for the catalytic process and 56.2 % for the non-catalytic process. Additionally, the reaction kinetic was determined and it was found to be a pseudo first order reaction. Activation energies were calculated from the Arrhenius equation.