Double metal cyanide (DMC) complexes are well-known heterogeneous catalysts for the polymerization of epoxides and the synthesis of propylene oxide based polyether polyols. In this study, to develop commercial catalyst systems for the polymerization of propylene oxide (PO), we describe a simple but very effective synthesis pathway for producing efficient DMC catalysts. We have investigated another mono-alcohols as alternative complexing agents (CAs) of the DMC complexes to tert-butyl alcohol (TBA). Besides that, we also have employed green DMC catalysts using vegetable oil based polyols as complexing agents for the synthesis of highly pure polyols. All the new DMC catalysts give a short induction time and very high activity. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermal gravimetric analysis and inductively coupled plasma optical emission spectroscopy. The total degree of unsaturation and the hydroxy values of the resulting polyols were measured. The molecular weight (MW) and polydispersity index (PDI) were analyzed using gel permeation chromatography in a tetrahydrofuran solvent. With new method, the total amount of metal salts and CAs consumed in the catalyst preparation procedure are significantly reduced compared to literature procedure. Comparing with the DMC catalysts using TBA as a CA in literature results for ring-opening polymerization of PO, all DMC catalyst prepared with mono-alcohols or vegetable oil based polyols as CAs give a very short induction time. These results make the production process of polyols energy saving, since the total period of production time can be significantly decreased. All the polyols produce a low level of unsaturation (lower than 0.013 meq g-1), moderate number average molecular weights (2200-6000 g mol-1) and very narrow polydispersity values (1.01-1.16).