The properties of polyurethanes strongly depend on microstructure, functionality, and molecular weight of its initial polyol used. Therefore, in this work, microstructure of polybutadiene-ol, a pre-polymer used for producing special purpose polyurethanes was determined by two analytical methods: FTIR and MHz 1H NMR spectroscopy. In the FTIR method, after obtaining εi (molar absorption in each wavelength) of a specified polyol, the microstructure (trans, vinyl and cis content) of pre-polymer was measured by analyzing IR absorption bands in 966 cm-1, 912 cm-1, 725 cm-1 due to trans,1,2,-vinyl and cis configurations, respectively. In the 1H NMR spectrums of polyols, microstructure was determined using the ration of area peaks of various protons (alkylic, olefinic and methylenic) as well as signals at 2.3-3.5 ppm which indicate position of hydroxyl groups in the back-bone of the polyol. Determination by 1H NMR spectroscopy is easier and microstructure of the polyol obtained is more precise than the FTIR method. Finally we established an equation to convert values obtained by FTIR to NMR.