Highly sensitive and selective hydrogen sulfide (H₂S) sensors based on hierarchical highly ordered SnO₂ nanobowl branched ZnO nanowires (NWs) were synthesized via a sequential process combining hard template processing, atomic-layer deposition, and hydrothermal processing. The hierarchical sensing materials were prepared in situ on microelectromechanical systems, which are expected to achieve high-performance gas sensors with superior sensitivity, long-term stability and repeatability, as well as low power consumption. Specifically, the hierarchical nanobowl SnO₂@ZnO NW sensor displayed a high sensitivity of 6.24, a fast response and recovery speed (i.e., 14 s and 39 s, respectively), and an excellent selectivity when detecting 1 ppm H₂S at 250 °C, whose rate of resistance change (i.e., 5.24) is 2.6 times higher than that of the pristine SnO₂ nanobowl sensor. The improved sensing performance could be attributed to the increased specific surface area, the formation of heterojunctions and homojunctions, as well as the additional reaction between ZnO and H₂S, which were confirmed by electrochemical characterization and band alignment analysis. Moreover, the well-structured hierarchical sensors maintained stable performance after a month, suggesting excellent stability and repeatability. In summary, such well-designed hierarchical highly ordered nanobowl SnO₂@ZnO NW gas sensors demonstrate favorable potential for enhanced sensitive and selective H₂S detection with long-term stability and repeatability.