Poly(phosphoeter)s (PPE)s are a class of polymers possessing a high chemical functionality and biodegradability. Novel, glutamic acid based poly(phosphoeter)s were synthesized by the Steglich reaction. The developed synthetic approach allows controlling the composition and the structure of PPEs, and therefore their physical and colloidal properties. The studies on solubilization and cytotoxicity in vitro proved the potential of PPEs for drug delivery applications.