The effective rate constants were measured and the relative reactivity was determined for a wide range of bridge and bridgehead substituted mono- and polyalkyladamantanes, bicyclo[3.3.1]nonane, protoadamantane, homoadamantane, diamantane, and isomeric trimethylenenorbornanes in their reaction with nitric acid. The relative reactivity in nitroxylation of cage hydrocarbons was shown to be determined by the stability of corresponding carbenium ions, the intermediates of the process. It was found that the nitroxylation rates for the examined hydrocarbons linearly correlate with the solvolysis rates of the corresponding bromides.