Monoacylglycerols (MAG) are nonionic emulsifiers, widely used in food, pharmaceutical, and cosmetic industries. Besides the bulk applications in food and dairy industries, pure MAG are also of great interest in synthetic organic chemistry where they are used as synthetic intermediates and as chiral building blocks. Reaction routes for MAG production including direct esterification of glycerol and fatty acids, interesterification between glycerol and fatty acid esters, glycerolysis of TAG and glycerol, partial hydrolysis of TAG, as well as alcoholysis of TAG. During the past few years, extensive efforts have been made for high yield of MAG from the reaction systems, using either chemical or enzyme as catalysts. And strategies have been developed aiming at the increase of MAG selectivity. An overview is given for such strategies targeting on the increase of MAG yield from the reaction systems. In particular, the mesoporous siliceous framework porosity and the surface hydrophilicity of the heterogeneous catalysts, as well as the solvation within the reaction systems caused by reaction medium, are discussed carefully to clearly highlight how catalysts and reaction medium can help to increase the MAG selectivity (MAG selectivity in the present paper means selectivity to form MAG instead of DAG).