Several N-alkyl-Se-alkylselenocarbamates were prepared. The structure was confirmed by X-raydiffraction. N-Alkyl-Se-alkylselenocarbamates showed interesting NMR spectral features in 13Cand 77Se NMR. They could be explained by the equilibrium between the major s-trans and theminor s-cis forms. This assumption was confirmed by the theoretical calculations.