Organic functionalization of periodic mesoporous silicas (PMSs) offers a way to improve their excellent properties and wide applications owing to their structural superiority. In this study, a new strategy for organic functionalization of PMSs is demonstrated by hydrosilylation of the recently discovered "impossible" periodic mesoporous hydridosilica, meso-HSiO1.5. This method overcomes the disadvantages of present pathways for organic functionalization of PMSs with organosilica. Moreover, compared to the traditional functionalization on the surface of porous silicon by hydrosilylation, the template-synthesized meso-HSiO1.5 is more flexible to access functional-groups-loaded PMSs with adjustable microstructures. The new method and materials will have wider applications based on both the structure and surface superiorities.