Water-permeable hollow starch particles alter the rheological behavior of their granular suspensions. However, their thin shells can rupture limiting applications. In this study, we used amaranth starch as building blocks (1 μm) to craft a crosslinked superstructure. Pickering emulsions were used as the templates where starch coated the droplets. Emulsions were heated at 75 °C to induce interpenetration of the polymers followed by precipitation in ethanol to trigger colloidal fusion. Particles were then crosslinked by sodium tri-metaphosphate; hollow particles formed after the interior template was removed by hexane. When canola oil was used, the particles ruptured at pH 11.5 due to the repulsion between the strands. In contrast, palm oil, emulsified at 50 °C, formed a rigid core after cooling, locked the starch at the surface and retained the structure. The crosslinked colloidosomes were larger (89 μm) and had higher viscosity, and stronger stability. Particle sizes >100 μm were made and produced a higher processing volume. Gentle centrifugation to harvest the particles kept the shells intact. The hollow structure exhibited jamming transition above 10 w/w%, which could serve as a super-thickener. This work demonstrates that microarchitecture plays a critical role in shaping material functionality.