Abstract: A significant limitation to the use of bulk imprinted silica in catalytic applications has been due to the hydrophobic framework resulting from the materials synthesis process. We have recently synthesized a new class of bulk imprinted silicates with a hydrophilic framework, which circumvents these limitations. This required the development of a novel materials synthesis stategy that represents the first implementation of thermolysis to affect imprint removal. Imprinted sites consisting of up to two primary amines have been synthesized within hydrophilic microporous and mesoporous inorganic-oxide frameworks. The materials synthesis process has been characterized by multinuclear solid-state NMR spectroscopy, thermogravimetric analysis, mass spectrometry, potentiometric titration and probe molecule binding to the imprinted sites. The latter reveal a remarkable ability to bind polar molecules that are inaccessible using materials with a hydrophobic framework. Important repercussions of this new class of materials for the activation of molecules for catalysis will be demonstrated.