Ordered nanostructured materials and their porous counterparts are important for numerous applications in sorption and separation sciences, electrochemistry, catalysis, and photonics. They can be synthesized by introducing surfactant or amphiphilic polymer template(s) into the condensation stage of a developing solid. Understanding the pathways involved in the formation of these materials is of great interest and will help in the development of future synthesis schemes for designing nanomaterials with controlled nanostructures, pore sizes and shapes, and particle morphologies. In this work, the formation pathway of carbonaceous particles, with cubic-type ordered nanostructures, in the polymer amphiphile-templated hydrothermal condensation of sugar was investigated. A detailed transmission electron microscopy study revealed the initial formation of ∼50 nm sized nanoparticles and the structure attributable to assembled nanoparticles to form larger microparticle volumes. Small-angle X-ray scattering analysis showed the time-dependent development of the ordered structures in the carbonaceous particles. A dynamic stabilization-destabilization of the ordered phase was suggested through the analysis of the liquid crystalline gel-like matrix. The growing carbonaceous body inherited the final liquid crystalline phase, giving the microparticles a well-ordered cubic nanostructure. An additional internal domain texture was also revealed inside the microparticles. The proposed pathway will contribute toward establishing strategies for precisely manipulating nanostructured bodies as well as acquiring an in-depth understanding of the templated precipitations, including those in the natural systems.