Glycerolysis of triolein and rapeseed oil were carried out with base catalysts such as Cs-MCM-41, Cs-Sepiolite, MgO, and calcined hydrotalcites with different Al/Al + Mg ratios. A wide range of basicities were covered in order to extract active hydrogens with pKa values from 9 to 16. MgO and hydrotalcites with low Al content, basic enough to extract protons from aliphatic alcohols such as glycerol, are active and selective catalysts for glycerolysis. By optimizing the main process variables, such as temperature and the glycerol/oil ratio it is possible to obtain a high yield of monoglycerides as well as to meet the quality requirements established by the European Union.