Integrating stimuli-responsive nanoparticles (NPs) into shape-tunable hierarchical superstructures has emerged as a powerful way to fabricate smart materials. Here, we propose a robust strategy for the fabrication of sheet-like superlattices and hollow capsules by precisely tuning the interfacial tension of emulsion droplets containing pH-responsive gold nanoparticle building blocks, providing an efficient route to construct hierarchical superstructures with different applications.