United Nations Class-3 hazardous materials (hazmats) are basically liquid products and transported in road tankers under ambient temperature and atmospheric pressure. They are mostly flammables and some of them are toxic (e.g. benzene) as well. The spillages due to collision related incidents involving the road tankers, carrying such hazmats through highways, pose not only flammability hazards due to pool fire, flash fire and vapor cloud explosion (VCE), but create substantial toxic hazards also. The paper presents the risk-based study of route evaluation of two state highways and one urban city road in western India on account of transportation of class-3 hazmats, namely benzene, toluene, p-xylene, methanol, cyclohexane and acetone. A comparative evaluation of study routes was undertaken based on their societal risks presented in terms of F-N curves and assessed against HSE, UK as well as VROM, The Netherlands risk acceptance criteria. Societal risks contribution of cyclohexane to the overall flammability risk mainly VCE is found to be the highest followed by acetone and benzene compared to other study hazmats. This is due to highly explosive nature of cyclohexane resulting into vapor cloud explosion. While acetone and methanol pool fires are likely to cause larger area of damage compared to others, benzene supersedes others as far as toxicity risk is concerned and larger evacuation area is encountered, as it poses greater Immediately Dangerous to Life or Health (IDLH) distance than others. Besides, study of initial isolation distance following an accident in case of benzene tanker found that benzene spillage requires larger initial isolation distance than others and so are the day and night protective action zone distances. (C) 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.