A convenient method to prepare spherical microparticulate composite adsorbents is described. Molecularly imprinted crosslinked methacrylate polymers were copolymerized with preformed microparticulate support particles of trimethylolpropane trimethacrylate (TRIM) containing residual double bonds. The resulting composite adsorbent could be packed in HPLC columns after just a simple washing procedure and was used for efficient chiral separation of amino acid derivatives. The pore system of the TRIM-particles could be filled with large amounts of functional polymer. The enantioselectivity for the print molecule Boc-L-Phe-OH was in the same range as that obtained by traditional bulk phase molecular imprinting, while the performance in HPLC was improved, both in terms of efficiency and pressure stability. The effect of various degrees of crosslinking and of monomer concentration on polymer characteristics, such as porosity and specific surface area, and its impact on the structure of the final polymer is discussed as well as the chromatographic performance of the resulting matrices.