The problem of detecting true isokinetic relationships (IKR) relates primarily to the problem of reliable evaluation of Arrhenius parameters. Two approaches (discriminating and nondiscriminating) for evaluating Arrhenius parameters have been examined using modelled data to detect IKRs, The discriminating approach allows only for the detection of an IKR but not for unambiguously estimating the isokinetic temperature. The non-discriminating approach represented by the isoconversional method allows not only for detecting an IKR but also for determination of the isokinetic temperature, This may in turn be used to obtain information about the actual reaction pathway of the thermally induced process. The thermal decompositions of poly(ethyleneterephthalate) composites and of tetranuclear Cu(II) complexes with various ligands are used as experimental examples.