To develop efficient and stable photocatalysts for visible light pollutant degradation, hierarchical Z‐Scheme WO3/Bi2WO6 nanotubes have been rationally designed and fabricated via a combined electrospinning‐calcination process. Moreover, the morphology of as‐fabricated nanotubes could be tuned by the annealing temperature. Accordingly, the newly‐designed hierarchical Z‐Scheme system highly facilitates the separation and migration of photoinduced charge carriers, and enhances the broadened photoabsorption range and high redox capacity owning to the synergistic effects of WO3 and Bi2WO6. Meanwhile, the corresponding possible formation mechanism is proposed as well. Benefiting from the unique structural features, the optimized 550 °C‐WO3/Bi2WO6 nanotubes exhibit the remarkable photoelectrochemical activity and photocatalytic performance for degrading pollutant models (4‐NP and RhB), among which reaction rate is superior to 500 °C and 600 °C‐WO3/Bi2WO6 counterparts. This work may shed light on rational design and construction of hierarchical Z‐Scheme WO3/Bi2WO6 nanotubes for energy and environment‐related applications.