The combination of supercritical fluid extraction (SFE) with supramolecular solvents-based microextraction (SSME) has been developed for extraction and determination of diphenylamine (DPA) in the peel of fruit samples. High performance liquid chromatography (HPLC) coupled with ultraviolet (UV) detection was applied for determination of the DPA. The supramolecular solvent was produced from coacervation of decanoic acid aqueous vesicles in the presence of tetrabutylammonium (Bu4N+). In SFE-SSME procedure, the dehydrated samples were loaded into SFE extraction vessel and extraction was performed in a prescribed time. The extracted analyte was collected in 5 mL aqueous solution (pH = 3) and introduced to SSME. The effective parameters on the SSME efficiency were studied and optimized. The Taguchi orthogonal array (OAD) experimental design with an OA(16) (4(5)) matrix was employed to optimize the SFE conditions. The calibration plot was linear in the range of 0.5-7.0 mg kg(-1) and the limit of detection (LOD), based on S/N of 3 was 0.3 mg kg(-1). Interday RSDs% lower than 10.3%, and intraday RSDs% lower than 7.1% were obtained. Analysis of DPA in different fruit peel showed that the improved technique has great potential for extraction and determination of DPA in fruit samples. (C) 2015 Elsevier B.V. All rights reserved.