The properties of zeolitic and related materials highly depend on their pore dimensions and topology as well as the presence and nature of framework heteroelements. Here, we present detailed insights into prenucleating solutions of zeolitic materials using two different organic structure-directing agents (SDAs) in the presence of fluoride ions. The silicate speciation was analyzed by means of electrospray ionization mass spectrometry (ESI-MS), wherein the structures of the occurring species were proven to depend on the nature of the used organic SDA. In addition, MS/MS experiments were revealed as a powerful tool to obtain detailed structural insight into the occurring silicate oligomers. With this information, we were able to locate heteroelements, namely, germanium, within these species and, furthermore, to determine the structure-directing effects of the used organic SDAs.