A series of new ionic liquids based on sterically hindered decyl(tri-tert-butyl)phosphonium (DTBP) or decyl(tricyclohexyl)phosphonium (DCHP) cations were prepared using quaternisation of tri-tert-butyl- or tricyclohexylphosphine with decylbromide and subsequent bromide exchange with the weakly-coordinating anions BF(4)(-), PF(6)(-), SO(3)CF(3)(-), N(SO(2)CF(3))(2)(-). The salts obtained melt below 100 degrees C and possess a broad electrochemical window. Density functional theory combined with X-ray crystallography, IR and Raman spectroscopy has been used to analyze the molecular and supramolecular structures of the compounds obtained and their possible influence on their physical properties.