First, previously unknown, cyclic organogermanium peroxides, 1,2,4,5,7,8-hexaoxa-3-germonanes, were synthesized by the reaction of 1,1′-dihydroperoxydi(cyclododecyl)peroxide with (di)alkyl(aryl)dihalogengermanes. The newcompounds have a higher tendency to undergo hydrolysis compared to silicon-containing analogs.