The friction sensitivity (FS) of five linear and eight cyclic nitramines has been determined. Arrhenius parameters of non-autocatalyzed thermal decomposition of these nitramines were used for comparison of the FS values with thermal reactivity. Generally, increasing values of activation energies of non-autocatalyzed decomposition of the studied nitramines are connected with decreasing FS values. A similar trend was found in the relation between FS and hypothetical initiation temperature for 5% conversion of the nitramines after 50 μs of their thermolysis, however, if in the given series of nitramines their initiation reactivity is predominantly determined by the energy content of their molecules and closer similarity of their molecular structures, then the above-mentioned trend may be opposite. The found relationships were used for prediction and verification of the activation energy of non-autocatalyzed thermal decomposition of 2,5-dinitro-2,5-diazahexane.