The ubiquity of micro-/nanoplastics poses a visible threat to the environment, aquatic organisms, and human beings and has become a global concern. Here, we proposed a liquid interface-based strategy using surface-enhanced Raman spectroscopy to coassemble nanoplastics and gold nanoparticles into a dense and homogeneous plasmonic array, thereby enabling the rapid and sensitive detection of trace nanoplastics. In addition, due to the uniqueness of the oil−water immiscible two-phase interface, we achieved ideal results for the detection of nanoplastics in a complex matrix (e.g., aqueous environment and edible oil) with a detection limit of μg/mL. With the aid of the principal component analysis algorithm, the differentiation and identification of multiple nanoplastic components (e.g., polystyrene, polyethylene, and polyethylene terephthalate) in aqueous environments and common hazards (e.g., Bap and Phe) in edible oil were achieved. Therefore, our self-assembled plasmonic arrays are expected to be used for monitoring environmental pollution and food safety.