Aqueous solutions of hydrophilic polymers and charged polysaccharides are known to have variety of microstructures. In this work, we show microstructures formed on the surface of poly vinyl alcohol (PVA) and hyaluronic acid (HA) blend gels. At specific hyaluronic acid composition in the blend, when PVA is crosslinked to form gels, both these polymers phase separate. This crosslinking reaction induced phase separation was examined by varying the moisture contents in the hydrogels. We also examine the precursor PVAHA blend solutions to highlight the origins of self-assembled structures. The evolution of microstructure domains leads to the formation of different shapes, such as sphere like particles to rod like assemblies on the surface. Such phase separation can be used to synthesize particles of different shapes and sizes.