One–dimensional (1D) heterostructures are promising for the fascinating physical/chemical properties. However, the selective deposition of innovative materials as efficient active sites on the backbone material is still challenging and meaningful. Herein, a universal strategy is presented to synthesize the novel 1D heterostructure, which is constituted of Mn₃O₄ nanowires (Mn₃O₄ NWs) and nano–sized Zn₂SnO₄ subunits with controllable morphologies including Zn₂SnO₄nanorods (Zn₂SnO₄ NRs), Zn₂SnO₄ nanocubes (Zn₂SnO₄ NCs) and Zn₂SnO₄nanooctahedrons (Zn₂SnO₄ NOs). The 1D Mn₃O₄/Zn₂SnO₄ heterostructure is proved to generate abundant surface adsorbed oxygen molecules to modulate the sensing activity in chemical sensors (CSs) for application in the acetone vapor detection. The developed gas sensor shows enhanced responses, ultrafast response time and great stability. The selective deposition method and interface engineering will open up an avenue to design the heterostructured nanomaterials for high–performance CSs and other potential applications.