Alkylguanidinium and alkylamidinium hydroxides have been developed as new basic ionic liquids for the first time from cyclic guanidine (TBD) and amidines (DBN, DBU). The method of preparation of [bmim]OH decribed in the literature was adopted for the synthesis of new ionic liquids. Synthesis was carried out using cyclohexane as the solvent for the synthesis of alkylguanidine and alkylamidine bromides. Anion metathesis was carried out over anionic resins in water as solvent. The structures of the new ionic liquids were confirmed by spectral analysis. The catalytic activity of the new ionic liquids was tested in transesterification of fatty acid methyl esters with trimethylolpropane, neopentyl glycol and 2-ethylhexyl alcohol.