Morphology, molecular weight, polydispersity, functionality, and thermal properties are important characteristics when using polyglycerol as a building block in the development of materials for industrial applications such as hydrogels, surfactants, asphalts additives, cosmetics, pharmaceutical, biomedical, and drug delivery systems. In this study several experimental techniques are used to understand the effect of process variables during synthesis in the catalyzed etherification of glycerol, a coproduct of biodiesel industry. Biobased polyglycerol is a high-valued product, which is useful as building block material because of its remarkable features, for instance, multiple hydrophilic groups, excellent biocompatibility, and highly flexible aliphatic polyether backbone. A connection between polyglycerol characteristics and process variables during synthesis allows the control of glycerol polymerization through reaction conditions. We show that temperature and catalyst concentration can be tuned with the aim of tailoring fundamental polyglycerol parameters including molecular weight, polydispersity, morphology, and functionality.