The characteristics of the polyalkylene oxide polyether polyols highly influence the properties of final polyurethane products. As a novel approach, in order to gain structural information, the recently invented data mining procedures, namely the Mass-remainder analysis (MARA) and the Multistep Mass-remainder analysis (M-MARA) are successfully applied for the processing of tandem mass spectrometry (MS/MS) data of various industrially important polyether polyols. M-MARA yields an ultra-simplified graphical representation of the MS/MS spectra and sorts the product ions based on their double bond equivalent (DBE) values. The maximum DBE values unambiguously differentiate among the various polyether polyols. Accordingly, the characteristic DBE values were 0, 1 for the linear diol polyethers, 0, 1, 2 for the three-arm, and 0, 1 2, 3, 4 for the six-arm polyether polyols. In addition, it was also found that the characteristic collision energy necessary for the optimum fragmentation yield depended linearly on the molecular weight of the polyols. This relationship offers an easy way for instrument tuning to gain structural information.