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A straightforward approach to recycle waste expanded polystyrene (EPS) foam to produce polystyrene (PS) microfibers using the improvised centrifugal spinning technique is demonstrated in this work. A typical benchtop centrifuge was improvised and used as a centrifugal spinning device. The obtained PS microfibers were characterized for their potential application for oil adsorption. Fourier transform infrared spectroscopy results revealed similarity on the transmission bands of EPS foam and PS microfibers suggesting the preservation of the EPS foam’s chemical composition after the centrifugal spinning process. Scanning electron microscopy displayed well-defined fibers with an average diameter of 3.14 ± 0.59 μm. At the same time, energy dispersive X-ray spectroscopy revealed the presence of carbon and oxygen as the primary components of the fibers. Contact angle (θCA) measurements showed the more enhanced hydrophobicity of the PS microfiber (θCA = 100.2 ± 1.3°) compared to the untreated EPS foam (θCA = 92.9 ± 3.5°). The PS microfiber also displayed better oleophilicity compared to EPS foam. Finally, the fabricated PS microfibers demonstrated promising potential for oil removal in water with a calculated sorption capacity value of about 15.5 g/g even at a very short contact time. The fabricated PS fiber from the waste EPS foam may provide valuable insights into the valorization of polymeric waste materials for environmental and other related applications.