In this study, a facile one-step method combining the pore expansion and the enlargement of the hollow cavity of hollow periodic mesoporous organosilica spheres (HPMOSs) into one step was proposed. Moreover, the whole process for the formation just needs 1 h and involves reaction just under normal pressure and temperature. We further investigate the influence of different expanders and the amount of expanders on pore size and hollow cavity size. The obtained HPMOSs using tridecane as expander possess excellent properties, including good spherical morphology, large hollow structures, radially oriented mesochannels (3.44 nm), uniform particle size (115 nm), high BET surface area (1298 m(2)/g), and large pore volume (1.96 cm(3)/g). In addition, the hollow cavity size and the mesoporous size can be controlled via the modulation of tridecane amount. This method also provides a basis for synthesizing both large pore and the hollow cavity of functionalized, monodispersed HPMOSs.