Potassium iodide catalysis was applied for the synthesis of protected benzylhydrazines and hydrazinoacetic acid esters by the alkylation of protected hydrazines. Benzylic halogenides and halogenoacetic acid esters were employed as alkylating agents. In these syntheses the reactive alkyl iodide molecules were generated in situ from less reactive halogenides, which significantly accelerated the alkylation reaction. The effectiveness of potassium iodide catalysis was proved by experiments performed under the same conditions in the absence of this salt.