The kinetics of the partition process to solid phase microextraction fibres is often modelled using a stagnant layer model. Despite its usefulness, in some agitation systems such a model cannot be applied because the stagnant layer cannot be characterized precisely. Therefore, in this present study an alternative approach is introduced. Transport from the bulk medium to the fibre coating is simply modelled by a finite mass transfer coefficient instead of diffusion through a stagnant water layer surrounding the fibre. Intra-fibre transport is described by non-steady diffusion. The model is aimed at the analysis of SPME measurements in the kinetic phase for samples including a binding matrix. It was validated with experimental results of SPME measurements concerning the absorption kinetics of [³H]estradiol at different concentrations of bovine serum albumin (BSA) as a chemical binding matrix. The model provides excellent fits of the experimental data, resulting in an association constant (K_a) of estradiol for BSA of 5.66 × 10⁴ M⁻¹, which is similar to literature values and a fibre coating/bulk medium partition coefficient of 5.0 × 10³. The kinetics of extraction were studied with the model, showing that the rate-limiting step in the extraction process was the diffusion in the fibre. This finding rules out the possibility that the presence of the matrix itself in the diffusion layer affects the kinetics of estradiol uptake into the SPME fibre.