AbstractIt was shown in Part II of this series of articles that geopolymers synthesized with organic bases could be used as precursors to mullite and mullite + glass composites. A natural next step is to determine whether it is possible to synthesize materials outside the Al2O3·SiO2 and alkali oxide·Al2O3·SiO2 phase systems. Hence, the focus of this study was the use of geopolymer‐like processing to make preceramic bodies with magnesium, yttrium, and zinc aluminosilicate and silicate compositions. These preceramics were successfully fired into monolithic bodies of cordierite, mixed yttrium and aluminum silicates, yttrium disilicate, and willemite. The synthesis of these preceramics employed a guanidine silicate solution, a synthetic oxide powder, and in some cases metakaolin to reach the oxide composition of the ceramic. All solidified within 3 days at 20°C or 50°C, depending on the composition. For the first time, this study showed that Y2O3 and ZnO can react with silicate solutions to give some Y‐O‐Si and Zn‐O‐Si bonding analogous to Al‐O‐Si bonding in geopolymers. These results suggest that other silicate compositions may be possible, such as with the rare earth oxides, which might be valuable to process like a geopolymer rather than by traditional ceramic processing. However, the ceramics made here were generally porous due to the expansion of gases within the sample that were trapped by a viscous liquid phase during firing.