Electrospinning is an effective way to fabricate ultralong nanotubes with a large surface area. However, the nanotubes synthesized through this way suffer from difficult controlling of structural parameters. A facile strategy for constructing highly controllable Pt@ZnO nanoparticles (NPs) drive TiO2 nanotubes (NTs) (Pt@ZnO-TiO2 NTs) was developed in this work. First, the polystyrene electrospun nanofibers 490 nm) containing Pt@ zeolitic imidazolate framework-8 (ZIF-8) was fabricated as a self-sacrificial template and then was decorated by a thinner tetrabutyl orthotitanate layer through soaking. After annealing, the Pt@ZnO NPs were obtained due to the decomposition of Pt@ZIF-8 during calcination. The involving of ZIF-8 can effectively prevent the aggregation of Pt during heat treatment (similar to 3 nm, monodispersed), and thus highly improves its catalyst property. When Pt@ZnO-TiO2 NTs were evaluated as a sensing material for toluene detection, the obtained sensors exhibited an enhanced sensing response (11.1 to 1 ppm toluene), faster response/recovery times (7.5 and 20.1 s) and a lower detection limit (23 parts per billion) during dynamic measurement, when compared to the pristine TiO2 and directly mixed Pt-TiO2 NTs. This was mainly attributed to the improved oxygen vacancy concentration in the NT composite and resistance modulation effect induced by the unique NT structure, as well as the well-dispersed and small-sized Pt catalyst.