Shape-selective pores have been synthesized in bulk silica via imprinting. The synthetic approach relies on a sol-gel process to immobilize the imprint within a hybrid organic/inorganic material. Cleavage of the carbamate linkage from this material generates a primary amine within a microporous binding site. Characterization studies, including potentiometric titration and solid-state nuclear magnetic resonance spectroscopy, indicate that most imprinted amine sites are accessible during binding with small molecule probes. However, larger probes are unable to adsorb to the same material, indicating significant shape-selectivity in binding. Additionally, an investigation of framework pore size effects in a catalytic system shows that shape-selectivity can be solely a result of the imprinted active site and not the framework structure.