Semiconductor heterostructures often have unique and/or enhanced physical and chemical properties compared to their respective counterparts, and hence have been extensively explored for their promising applications such as in electronic storage devices and photocatalysts.1−3 For example, semiconductor heteronanostructures can not only prominently increase light-harvesting efficiency but also promote charge separation and transfer effectively, leading to improved photocatalytic activity.4−11 Porous nanostructures of hybrid materials with uniform morphology and good structural stability have also attracted considerable interest owing to their high specific surface area and widespread applications in many different fields.12−14 However, despite some successful preparation of porous heteronanostructures,15,16 tailored synthesis of porous heterostructures toward practical photocatalytic applications is still very limited, especially due to the structural incompatibility between hybrid materials. It is therefore a great challenge to develop facile and reliable strategies to produce porous heterostructured semiconductor materials.17,18 With unique optical properties and hierarchical structures, bismuth compounds and their composites have attracted tremendous attention for their heterogeneous photocatalysis applications.19−21 As an example, monoclinic scheelite bismuth vanadate (m-BiVO4), with a narrow band gap of 2.4 eV, is an important visible-light responsive photocatalyst, which has been