Abstract. Reaction with the hydroxyl (OH) radical is the dominant removal process for volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for reactions of OH with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models, and are required more generally for impact assessments involving the estimation of atmospheric lifetimes or oxidation rates for VOCs. Updated and extended structure–activity relationship (SAR) methods are presented for the reactions of OH with aliphatic organic compounds, with the reactions of aromatic organic compounds considered in a companion paper. The methods are optimized using a preferred set of data including reactions of OH with 489 aliphatic hydrocarbons and oxygenated organic compounds. In each case, the rate coefficient is defined in terms of a summation of partial rate coefficients for H abstraction or OH addition at each relevant site in the given organic compound, so that the attack distribution is defined. The information can therefore guide the representation of the OH reactions in the next generation of explicit detailed chemical mechanisms. Rules governing the representation of the subsequent reactions of the product radicals under tropospheric conditions are also summarized, specifically their reactions with O2 and competing processes.