This paper presents a new approach for the spectral study of geminate charge carrier production in organic liquids. The ionisation yields and effective cross-sections of methanol and ethanol, taken as model systems of the polar protic solvents, are obtained experimentally, between 6 and 10.6 eV, under synchrotron monophotonic radiation; Experimental results are presented for the first time which allow a detailed description of the primary processes involved in the ionisation of these liquids. (C) 2002 Elsevier Science B.V. All rights reserved.