A simple and versatile method for the synthesis of substituted 1,5-benzodiazepines on MTSA-Neutral Al2O3 in the solid state is reported. The substituted 1,5-benzodiazepines were prepared by the three component reaction of substituted aldehydes, substituted acetophenones and o-phenylenediamine in the solid state. The chemical structure of the newly synthesized compounds has been confirmed by IR, 1H NMR, mass spectra and elemental analysis.