A novel method to rapidly methylate glycerol and generate products having greater value has been demonstrated using tetramethylammonium hydroxide (TMAH) thermochemolysis. Through analysis with GC–MS, it is shown that the reaction between TMAH and glycerol at elevated temperatures produces a series of mono, di and tri-methoxylated glycerols with potential applications as organic solvents. While other methylation reactions can only be carried out in batch reactions, thermally assisted methylation using TMAH can be performed in a continuous flow process.