The biological activity of skin-sensitising chemicals is related to their ability to react either directly or after metabolic activity with appropriate skin proteins. For direct-acting electrophilic compounds, this ability can be modelled by the Relative Alkylation Index (RAI) by a combination of electrophilicity and hydrophobicity parameters. Several SARs based on this approach are reported. In this present work, electrophilicity parameters based on Taft substituent constants are used together with Leo and Hansch log P fragment values to calculate RAI values for hard electrophiles having a reactive carbonyl group. These are then applied to analysis of sensitisation data obtained in the murine Local Lymph Node Assay (LLNA) for two series of diketones as well as a homologous series of alpha, beta-unsaturated aldehydes. The sensitisation potentials of these reactive electrophiles show good correlations with the RAI. These findings re-affirm the view that physicochemical parameters are the key to eliciting the relationship between chemical structure and a toxic endpoint. They provide further evidence of the value of SAR studies in identifying mechanisms of sensitisation and aiding risk assessments without the need for extensive animal testing.