Hydroxyl value and primary hydroxyl relative content of polyether polyol were determined by near-infrared(NIR) spectroscopy using a common glass vial as a sample container. Compared with those from conventional analysis, the overall prediction results are comparatively satisfying(R2(HV)=0.9941, R2(PHC)=0.9930). It can be utilized as a simple and fast quality analysis method in actual industrial production.