The formation of phenylene-bridged periodic mesoporous organosilicas (PMOs) in the presence of three diblock copolymers differing in hydrophobic hydrocarbon chain lengths was investigated. Hexaethylene glycol octadecylether (C-18(EO)(6)), hexaethylene glycol hexadecylether (C-16(EO)(6)), and hexaethylene glycol dodecylether (C-12(EO)(6)) were chosen in order to obtain insight on the influence of the hydrocarbon chain length on the mesostructure. 1,4-Bis(triethoxysilyl)benzene (BTEB) was used as organosilica precursor under mild acidic conditions. The reactions were followed by in situ small-angle X-ray diffraction (SAXD) on-time in a capillary flow setup. It was found that during the reaction the formation of different structures was observed, which is ascribed to the hydrolysis and condensation of the organosilica precursor. In all cases, different structures evolve with time and phase transitions are observed during the measurements independent of the hydrocarbon chain length.