Hypothesis: Molecular extraction efficiency can be boosted with the assistance of nanoparticles (NPs). It is based on adsorption of the extractants in one phase and desorption in another phase, which requires a reversible phase transfer of the NPs. Experiments: We synthesized the gold@poly(N-isopropylacryamide) (Au@PNIPAM) NPs via an interfacial self-assembly method enhanced by post-polymerization. We adopted Rhodamine 6G (R6G) as the model molecule for the extraction test. In comparison, UV-Vis extinction spectra were recorded to monitor the extraction processes with or without the Au@PNIPAM NPs. We further analyzed theoretically with thermodynamics and first-principle calculations. Findings: The hybrid Au@PNIPAM NPs show a reversible phase transfer between the interface and chloroform phases. The Au NPs assisted extraction efficiency of R6G shows 5 times higher than that without Au NPs. The thermodynamic analysis of the nanotransportation system agrees well with the ab initio density functional theory calculations. This nanoparticle-assisted molecular transportation modifies the extraction kinetics significantly, which will provide further implications for biphasic catalysis, pollutant treatment and drug delivery. (C) 2020 Elsevier Inc. All rights reserved.