A multi‐molybdate coordination‐polymer‐precursor route was developed to synthesize mesoporous MoO3 nanoribbons. In this reaction process, the coordination‐polymer‐precursor (i.e., {Mo36} ions) was firstly synthesized, as proven by FTIR spectroscopy. By controlling the experimental conditions, the {Mo36} ions underwent a directed assembly process and a dehydration process to form 1D mesoporous MoO3 nanoribbons. HRTEM examination and BJH measurements demonstrated that the mesopores had an average diameter of about 3 nm in the nanoribbons. As a result of their mesoporous nature and their 1D nanostructure, the nanoribbons exhibited better selectivity, higher sensor response, and lower working temperature to H2S gas compared with previously reported1D MoO3 nanostructures.