Stricter and ever increasing environmental legislations and demand for higher quality products are the driving forces for the refiner in an attempt to characterise the refining streams on the molecular basis. The objective of this work is to develop a new methodology to interrelate the bulk properties and molecular information of the refining streams in order for refiners to look at the contribution of each molecular group on the properties of the refining streams. The molecular information of a particular refining stream is presented in the form of MTHS (molecular type homologous series) matrix representation [Peng, B., 1999. Molecular modelling of petroleum processes. Ph.D. Thesis, UMIST]. To enhance the accuracy and usability of the method, structural contribution of each isomer on various properties such as octane number, and reid vapour pressure, etc. are considered. Structural lumping rules are then applied to obtain the physical properties of each homologous series. Databases are set up for the properties and molecular information of typical refining streams. Automatic selection of sample matrices through linear combination is used to predict new composition matrices. The methodology is illustrated for refining streams with gasoline range hydrocarbons. The properties predicted based on the new methodology proves to be within 5-6% error range. (c) 2005 Elsevier Ltd. All rights reserved.