Characterisation of petroleum fractions is the systematic analysis and representation of composition and properties of petroleum fractions. Characterisation methods play an important role in understanding of the physical and chemical behaviour of a petroleum fraction, its individual constituents, and are essential for modelling of refinery processes. In order to comply with the current and future product specifications for cleaner fuels, refineries are employing new processing technologies and more severe operating conditions in existing operating units. Consequently refinery process models are required to capture the chemistry of conversion processes employing characterisation of petroleum fractions at molecular level. In this paper a review of the conventional characterisation methods used for modelling of refinery processes is presented. The molecular type and homologous series (MTHS) matrix representation of petroleum fractions is discussed in detail. The previous work on MTHS matrix representation approach is limited to light petroleum fractions such as gasoline, and takes into account only hydrocarbon molecules. These shortcomings of MTHS matrix representation approach are addressed in this work through the development of a new strategy for estimation of composition and properties of petroleum fractions. (C) 2010 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.