The determination of octanol-water partition coefficients (log KOW) is important for the prediction of the fate of organic pollutants in the environment. Traditionally, log KOW values are determined by shake-flask, estimated by, e.g., HPLC retention data, or calculated, e.g., from ClogP. In this paper, an alternative approach is reported that allows log KOW, to be estimated from solid-phase microextraction (SPME) data. Previously reported attempts to correlate SPME data with log KOW are discussed. The results obtained in this work for six phenols, using an 85 μm polyacrylate-coated fiber, indicate that SPME is a viable method for estimating log KOW values <3.5.