Hybrid nanomaterials with controlled dimensions, intriguing components and ordered structures have attracted significant attention in nanoscience and technology.Herein, we report af acile and green polyoxometallate (POM)-assisted hydrothermal carbonization strategy for synthesis of carbonaceous hybrid nanomaterials with molecularly dispersed POMs and ordered mesopores.B yu sing various polyoxometallates such as ammonium phosphomolybdate,s ilicotungstic acid, and phosphotungstic acid, our approach can be generalized to synthesize ordered mesoporous hybrid nanostructures with diverse compositions and morphologies (nanosheet-assembled hierarchical architectures,nanospheres,and nanorods). Moreover,t he ordered mesoporous nanosheet-assembled hierarchical hybrids with molecularly dispersed POMs exhibit remarkable catalytic activity toward the dehydration of tert-butanol with the high isobutene selectivity (100 %) and long-term catalytic durability (80 h).