In this article we report the successful synthesis of a new class of periodic mesoporous organosilicas (PMOs) with a urea-bridged organosilica precursor under acid-catalyzed and inorganic-salt-assisted conditions. The large-pore hybrid materials have an ordered mesostructure with uniform pore size distributions, excellent thick framework walls, thermal stability, and specific functional groups. The composition of the mesoporous organosilicas was characterized by FTIR spectroscopy, (13)C cross-polarization magic-angle spinning (CP MAS) NMR spectroscopy, and (29)Si MAS NMR spectroscopy.