First and second generation aliphatic polyether dendrons based upon poly(ethylene oxide) (PEO) peripheries have been prepared using a combination of a Williamson etherification and hydroboration/oxidation reactions. The purification after each synthetic step was performed by stepwise extraction, after which the reaction yields were found to be greater than 80%. The dendrons obtained showed narrow molecular weight distributions of less than 1.09, and this was confirmed by mass spectrometry and gel permeation chromatography. Since the synthesis procedure did not it was successfully scaled up to larger quantities. The hydrophilic non-ionic dendrons prepared by this straightforward method may be employed as building blocks in the design of functional soft materials such as ionic conductors and drug carriers.