This study demonstrates the synthesis of self-assembled hexagonal WO3 nanowire bundles, with both ordered and random structures in the presence of SO42− ions, by a simple but efficient solvent-thermal method. The as-synthesized products are composed of hierarchical bundles with assembled ultrathin nanowire subunits. The growth and assembly mechanisms, regarding WO3 nanowire bundles, may be elucidated through oriented attachment or Ostwald ripening growth, based on a synergistic effect from both oxalic acid and ethylene glycol in dehydrating WO3·xH2O to WO3 nanocrystals and in controlling segregation behavior, along with high surface areas (18.4 m2 g-1 for ordered structures while 11.6 m2 g-1 disordered ones), which makes WO3 bundles great potential for gas sensing. To further enhance gas sensing, gold nanoparticles were chosen to deposit on the surface of WO3 nanowire bundles by acting with amino groups linked with WO3 bundles in the HAuCl4 solution with further oxidation. The Au-WO3 composites were examined towards various reducing gases, with exemplary sensitivities of (S = 127, 82), (S = 72, 52) towards n-butanol and acetone, respectively. The sensing mechanisms of such WO3 bundle structures are further understood in detail. This work will make the unique WO3 bundle nanostructures highly potential for gas sensing applications.