The catalytic etherification of glycerol using calcium lanthanum oxide supported on MCM-41 as a stable heterogeneous basic catalyst was investigated. Stable heterogeneous mesoporous basic catalysts were synthesized by wet impregnation of MCM-41 with calcium nitrate and lanthanum nitrate. The surface and structural properties of the prepared catalysts were when characterized using different techniques. MCM-41 and modified MCM-41 were used in the solventless etherification of glycerol to produce diglycerol as the desired product. The reaction was performed at 250 degrees C for 8 h, and catalyst activity was evaluated. Catalytic etherification over the 20%Ca1.6La0.6/MCM-41 catalyst resulted in the highest glycerol conversion of 91% at the diglycerol yield of 43%. The distribution of diglycerol isomer in the etherification of glycerol was studied, and the value of the sum of two dimers (beta beta' + alpha beta = 67%) was found to be higher than that of alpha alpha' dimer (33%) after 8 h of reaction. Thus, the major reaction occurred inside the porous area instead of the external surface area. (C) 2014 Elsevier B.V. All rights reserved.