Methylated β-cyclodextrin was used to complex the hydrophobic monomers n-propyl acrylate (1), n-butyl acrylate (2), n-pentyl acrylate (3), n-hexyl acrylate (4), and cyclohexyl acrylate (5) respectively yielding the corresponding water-soluble host/guest-complexes 1a-5a. The complexes were polymerized in water by free radical mechanism and the initial polymerization rates (v 0) determined. We found that v0 increases as follows: 1a (12.5), 2a (27.5), 3a (44.2), 5a (49.4), 4a (75.8 × 10 -6 mol‚L -1 ‚s -1 ). To investigate the influence of the hydrophobic character of the guest monomers on the reaction rate, the water solubilities of the uncomplexed monomers 1-5 were determined by HPLC measurements. It was generally shown that with increase of water solubility of the free monomers the initial reaction rate (v0) decreases significantly.