We propose a new spectral study of the ionisation of liquid cyclohexane, 2,2,4 trimethylpentane and tetramethylsilane excited by single photons of synchrotron radiation in the vacuum ultraviolet. Ionisation yields and effective cross-sections are obtained, between 6 and 10.8 eV excitation energy, and compared to the absorption and photocurrent spectra in the same spectral region. In addition to the well-known conduction band states, the existence of charge transfer states in the band gap is evidenced for the first time. (C) 2003 Elsevier B.V. All rights reserved.