The catalytic activity of the walnut shell ash was investigated in the biodiesel production by the sunflower oil methanolysis. The catalyst was characterized by the TG-DTA, XRD, Hg porosimetry, N₂ physisorption, SEM, and Hammett method. In addition, the effects of the catalyst loading and the methanol-to-oil molar ratio on the methyl esters synthesis were tested at the reaction temperature of 60 °C. The walnut shell ash provided a very fast reaction and a high FAME content (over 98%). As the reaction occurred in the absence of triacylglycerols mass transfer limitation, the pseudo-first-order model was employed for describing the kinetics of the reaction. The catalyst was successfully reused four times after the regeneration of the catalytic activity by recalcination at 800 °C.