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Phase separating systems present a unique opportunity for designing composites with hierarchical microstructure at different length scales. We report here our success in synthesizing phase separating metallic glasses exhibiting the entire spectrum of microstructural possibilities expected from a phase separating system. In particular, we report novel core shell and hierarchical structures of spherical glassy droplets, resulting from critical wetting behavior and limited diffusion. We also report synthesis of a bulk phase separating glass in a metallic glass system. The combination of unique core shell and hierarchical structures in metallic glass systems opens a new avenue for the microstructure design of metallic glasses.