We report the unusual aqueous (micro) phase separation of binary mixtures of two biocompatible, hydrophilic homopolymers and the corresponding double-hydrophilic diblock copolymers of poly (ethylene oxide) (PEO) and poly[2-(methacryloyloxy) ethyl phosphorylcholine) (PMPC). SAXS analysis of these double hydrophilic block copolymers in concentrated aqueous solution shows highly hydrated nano-structures and a hydration mechanism is proposed based on these data.