In this paper, biosorption-based dispersive liquid–liquid microextraction (BioDLLME) incombination with magnetic solid-phase extraction (MSPE) has been developed as a sam-ple pretreatment method with high enrichment factor for the sensitive determinationof ibuprofen in water samples. At first, magnetic Fe3O4/polypyrrole nanoparticles weresynthesized and employed as sorbent for the MSPE of ibuprofen. After the elution ofthe desired compound from the sorbent by using methanol, BioDLLME technique wasperformed on the obtained solution. After MSPE, the eluent of MSPE was used as the dis-perser solvent for BioDLLME, so that the extra preconcentration factor could be achieved.The properties of the prepared magnetic sorbent were characterized using field emissionscanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffrac-tion methods. Experimental parameters affecting the extraction efficiency were studiedand optimized. Under optimum conditions, the enrichment factor was 274. The linear dy-namic range and limit of detection are 0.25–80 and 0.083g/L, respectively. The relativestandard deviations for six replicate measurements are 3.82%.