The integration of Pickering emulsion as a versatile template facilitates the assembly of nanoscale and microscale NPs, leading to the formation of intricate 3D superstructures. These superstructures exhibit collective properties, including optical, electric, and catalytic functionalities, surpassing individual building block. This review comprehensively explores the design and engineering principles behind the creation of these multifaceted superstructures. The exploration begins with the fundamental aspects of surface chemistry governing nanoparticles, a crucial factor in directing their assembly behavior at the curved liquid–liquid emulsion interface. Emphasis is placed on understanding emulsion stability, a pivotal element guiding the formation of stable 3D architectures. The discussion extends to unraveling the underlying mechanisms promoting the formation of these 3D superstructures. The focus lies in elucidating the optical functionalities of these superstructures, particularly in the context of surface-enhanced Raman spectroscopy application. The surveyed literature showcases diverse Pickering emulsion-based strategies employed in the assembly of plasmonic nanoparticles into intricate superstructures, offering controlled architectures and unlocking unique potentials for chemical and biochemical sensing.