Optically active (α)-monobenzoate glycerol ((α)-MBG) is known to be a useful starting compound for the preparation of chiral drugs, such as β blockers, platelet activating factor and (S)-carnitine [1]. The reaction consists in an enzymatic asymmetric esterification of benzoic acid in the α-hydroxil group of glycerol. Figure 1 shows the reaction system. The activity, stability and operational selectivity of lipases as a catalyst in organic synthesis can be controlled by immobilization and the reaction media [2]. There are many strategies of immobilization, which promote differents ways of enzyme orientations that could modulate the enantioselectivity. For this purpouse, support with different activation, as hydrophobic and epoxide groups, allow enzyme immobilization by adsorption and/or covalent attachmente [3]. The present work was focused to studied the enantioselectivity of the esterification reaction to produce (R)-MBG in 1, 4 dioxane evaluating the effect of lipase orientation during the immobilization according to support used and the substrates ratio in the reaction.