An efficient method for the synthesis of benzannelated macrocyclic di- and triperoxides by cyclocondensation of phenol, catechol, resorcinol or hydroquinone with bis-hydroperoxides and formaldehyde in the presence of lanthanide catalysts has been developed. Additionally, by using flow cytometry, it has been shown for the first time in this work that thus-synthesized macrocyclic di- and triperoxides are efficient apoptosis inducers in the tumor cultures Jurkat, K562 and U937 and in fibroblasts.