Well-defined poly(ethylene oxide)s with a primary amino group at one end and a hydroxyl group at the other terminus were synthesized with new sila-protected amino functionality initiator, potassium N-[2-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-ethyl]methyl amide [1b]. 1b initiated an anionic polymerization of ethylene oxide (EO) to form a polymer (PEO) without any side reactions such as a cleavage reaction of protective group and a chain transfer reaction. The molecular weights of the PEO determined from GPC and MALDI TOF-MS spectrometry agreed well with those from end group analysis using 1H and 13C NMR and TLC and also with the expected value from EO/initiator ratio. From these results, it was concluded that the polymers thus obtained had a primary amino group at one end and a hydroxy group at the other end and can be regarded as hetrobifunctional PEO.