Abandoned landfills and dumps, where untreated waste materials were deposited in the past, are a main anthropogenic source of relevant gaseous emissions. The determination of stability is a crucial target in the context of landfill risk assessment. FTIR spectroscopy and simultaneous thermal analysis in association with multivariate statistical methods were applied to landfill materials in order to get information on the kind of waste and its reactivity. The spectral and thermal patterns are fingerprints of the material. Industrial waste and the material from a 5-year-old reactor landfill were distinguished from the defined classes of mechanically–biologically treated (“MBT”) waste and 30 to 40-year-old stable landfills containing municipal solid waste and construction waste (“LF”) by a classification model based on soft independent modeling of class analogy (SIMCA). Degradation experiments were carried out with the fresh material originating from one MBT plant that was subjected to aerobic and anaerobic conditions in lab-scale reactors. These samples were compared to samples of one reactor landfill and to the landfill fraction from the MBT plant to demonstrate the efficiency of the biological pretreatment before final disposal. Prediction models that are based on spectral or thermal characteristics and the corresponding reference analyses were calculated by means of a partial least squares regression (PLS-R). The developed models of the biological oxygen demand (BOD) and the dissolved organic carbon (DOC) were based on spectral data, the models of the total organic carbon (TOC) and total nitrogen (TN) were based on thermal data (heat flow profiles and mass spectra of combustion gases). Preliminary results are discussed. The enthalpy of the materials decreases with progressing mineralization, whereas the enthalpy of the remaining organic matter increases. The ratio of the enthalpies was used as an indicator of stability. Selected samples comprising old landfills, a recent reactor landfill, MBT landfills and MBT materials were classified according to the calculated ratios.