Lithium and n-alkylamine molecules containing 1-16 carbon atoms were intercalated into layered vanadium diselenide. The reaction with amines is favoured by prior lithium intercalation. Alkylamines form double layers in the interlayer space between consecutive VSe2 slabs. Also, lithium is not exchanged with alkylammonium ions, but is largely retained in the form of solvated ions. The angle between the amine molecules and the host lattice layers is constant for the solvated ions but increases gradually with the size of the organic molecules in the alkylamine intercalates.