As a new diol, poly(oxyalkylene-alt-PPO) glycols including the methylene-oxy group from polypropylene glycol (PPG) were newly synthesized by the phase transfer catalysis. Waterborne polyurethanes (WPUs) with different contents of the modified polyol as a soft segment were synthesized. We investigated the possibility of their application for optical film materials. Comparing to PPG-based WPU, the Tg of poly(oxyalkylene-alt-PPO) glycols-based WPU increased and the refractive index and the pencil hardness were higher than those of PPG-based WPU while the optical transmittances were almost the same. These indicate that poly(oxyalkylene-alt-PPO) glycols-based WPU can be used for optical protect film.