Analyte-triggered nanoparticle (NP) assemblies in bulk colloidal suspension have been extensively utilized in various optical sensors. Nevertheless, the assembling process is still limited by the slow diffusion dynamics of NPs and the low concentration of analytes in trace detections, which hinders further improvement of the sensitivity and repeatability of the sensors. In this work, by functionalizing the gold NPs with specific ligands, we constructed a dual-mode optical sensing platform for multianalytes based on the plasmonic NP array at the liquid-liquid interface. Through emulsification, the NP diffusion kinetics are boosted for several orders, and the NPs are condensed from the bulk aqueous phase to the liquid-liquid interface as a plasmonic array. The as-formed metasurface generates major reflectance and surface-enhanced Raman scattering changes in response to analytes, providing two optical sensing modes. As prototypes, cysteine and glucose are selected as the target molecules, achieving the limit of detection as 193 ± 2 and 297 ± 12 pM, respectively.