The use of glycerol from biodiesel industries to produce high value-added products would increase the competitive potential of biodiesel producers. The present work investigates the production of glycerol ethers, a diesel and biodiesel additive. A single reactive distillation is proposed to overcome the low glycerol conversion and product yield that limit a conventional process. The theoretical performance of the reactive distillation is analyzed taking glycerol conversion and the glycerol ether yield into consideration. The simulation results show that the glycerol and mono-tert-butyl ether of glycerol are completely used in the reactive stages and thus, the recycle section by which glycerol and the mono-tert-butyl ether of glycerol are recovered is unessential. The parametric analysis for the reactive distillation is reported. Based on the process economic analysis from a total annual cost, the optimal reactive distillation configuration for glycerol ether production consists of two rectifying stages, eight reactive stages and one stripping stage.