The synthesis of poly(ethylene oxide) (PEO) with amino end group, a key functionality for PEGylation, is a long-standing challenge. Multistep routes based on postmodification or covalent protection have been adopted to circumvent ethoxylation of the amino group by ethylene oxide (EO). Here, we report a noncovalent protection strategy for one-step synthesis of PEO amine. An amino (di)alcohol is mixed with a small amount of mild phosphazene base and excess triethylborane (Et3B) before addition of EO. The complexation of the amino group with Et3B guarantees that polymerization of EO occurs selectively from the hydroxyl group through the bicomponent metal-free catalysis. Simply by precipitation in diethyl ether, the protective Et3B as well as the catalyst can be removed to afford α-amino-ω-hydroxyl PEO with controlled molar mass, low dispersity, and complete end functionality. The effect of initiator structure and retention of Et3B on the storage (oxidative) stability of PEO amine is also revealed.