A synthesis was developed of 2,5-dimethyl-2-tert-alkylperoxy-5-lithiumoxy-3-undecynes by treating the corresponding peroxyalkynes with butyllithium followed by reaction of the arising lithium peroxyacetylides with 2-octanone. The lithium peroxyalcoholates undergo hydrolysis with water to furnish peroxy bond containing alcohols. They also react with methyl and ethyl iodides, alkyl and benzyl bromides in the presence of hexamethylphosphoramide to afford the corresponding 2,5-dimethyl-2-tert-alkylperoxy-5-alkyl(benzyl)oxy-3-undecynes, with benzoyl chloride they yield peroxy bond containing benzoates. The thermal stability of the peroxides obtained was estimated by derivatography.