Symmetrically cyclic or acyclic substituted 1,2,4,5-tetraoxane (peroxide dimer) and 1,2,4,5,7,8-hexaoxonane (peroxide trimer) derivatives were synthesized, and their cetane numbers (CNs) were investigated to evaluate their viability for use as CN improvers. Tetraoxane and hexaoxonane derivatives were synthesized from five cyclic and acyclic ketones ranging from C6 to C8 to determine the impact of the carbon number of these substituents on the performance of the tetraoxane and hexaoxonane derivatives as cetane improvers. Chemical synthesis methods included acid-catalyzed cyclocondensation of ketones with gem-dihydroperoxide. In this study, CN performances of individual tetraoxane and hexaoxonane derivatives in the concentration range of 500−1000 ppm were investigated and compared to the traditional CN improver 2-ethylhexyl nitrate (2-EHN). Furthermore, the effects of different mixture compositions of tetraoxanes, hexaoxonanes, and 2-EHN on CN were studied in this research. The experimental results suggest that tetraoxane and hexaoxonane derivatives prepared from acyclic ketones with carbon numbers of 6 and 7 exhibited better performance than 2-EHN as an additive. The hexaoxonane derivatives provided better cetane improving capabilities than the tetraoxane derivatives.