The compact, nitrogen‐rich structure of 2,4,6,8,10,12‐hexaazaisowurtzitanes calls attention among researchers worldwide. These compounds have found the greatest utility as substrates for nitration to obtain the caged polynitramine, 2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane, which possesses a high‐energy performance. All new derivatives of hexaazaisowurtzitane are nitratable. The present study examined the nitration process of 2,6,8,12‐tetraacetyl‐2,4,6,8,10,12‐hexaazaisowurtzitane derivatives obtained through the condensation reaction with aldehydes under various conditions to yield CL‐20. The yield of CL‐20, a well‐known nitration product of hexaazaisowurtzitane compounds, was found to depend on the substrate structure and the nitrating mixture composition. The revealed dependence of the synthesis of various nitrated compounds on the holding time enables the synthesis of products with different physicochemical properties in a single process.