Most of the reported ternary oxides based sensors have not been realized to detect ppb-level H2S till now. In this work, Zn2SnO4 hierarchical quasi-microspheres were prepared through a facile surfactant-free hydrothermal method followed by calcination in air atmosphere. The quasi-microspheres are composed of nanosheets with the thickness of 100 nm and octahedra with the average size of 0.63 μm, respectively. The sensor fabricated from such Zn2SnO4 hierarchical quasi-microspheres shows excellent selective response to H2S at 133 °C with the lowest detection limit of 1 ppb. The gas response exhibits good linear relationship in the concentration range of 1-1000 ppb. Such outstanding H2S sensing property might be attributed to its porous structure, the synergistic effect of the two typical building blocks and the surface adsorbed oxygen, and the possible sensing mechanism is also discussed.