The interaction of estradiol, estrone, progesterone and testosterone with environmentally relevant concentrations of Aldrich humic acid, alginic acid and tannic acid was studied using solid-phase microextraction (SPME). Since bulk organic matter and certain hormones such as estradiol and estrone contain dissociable functional groups, the effect of pH on sorption was investigated as this will influence their fate and bioavailability. For humic acid and tannic acid, sorption was strongest at acidic pH when the bulk organic matter was in a non-dissociated form and decreased when they became partially negatively charged. At acidic and neutral pH the strength of partitioning was influenced by hormone functional groups content, with the strongest sorption observed for progesterone and estrone. At alkaline pH conditions, when the bulk organics were dissociated, sorption decreased considerably (up to a factor of 14), although the non-dissociated hormones testosterone and progesterone indicated greater sorption to humic acid at pH 10 compared to the partially deprotonated estradiol and estrone. This study demonstrates that SPME can be used to assess organic matter sorption behaviour of a selected range of micropollutants and at environmentally relevant organic matter concentrations.