The preparation of high capacity molecularly imprinted polymers (MIP) that could be used as antibody analogues is reported. A functionalised mesomorphous polysilaxane network built up around theophylline was synthesized. After extraction of the guest molecule, the network preserved the mesomorphic organisation set up in the presence of the template. Batch rebinding analysis, performed in the presence of theophylline or structurally analogous caffeine, revealed that the imprinted polymer has a significant selectivity towards the template and a greater capacity than both an unimprinted mesogenic network and an imprinted non mesogenic network.