||A series of polyether polyols has been synthesized by ring-opening polymerization (ROP) of various epoxides such as propylene oxide, 1,2-epoxy hexane, glycidyl isopropyl ether, and 1,2-epoxy tetradecane using Zn-Co double metal cyanide (DMC) catalysts. The DMC catalysts were characterized by structure-sensitive analysis (Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray powder diffraction) and elemental analysis (thermogravimetric analysis). In addition to propylene oxide, DMC catalyst exhibited high activity in the batch polymerization of epoxides both in the presence and absence of initiator. The resultant polymers had a wide range of molecular weight (Mn = 3000–13000) and polydispersity index (1.23–4.55). The functionality of the producing polyols can be controlled by using suitable initiators.