The objective of this study was to evaluate the Calotropis procera fiber treated with NaOH combined with heat treatment as sorbent material for removal of petroleum and derivatives in cases of oil spill. The effects of oil viscosity, fiber/oil contact time, and the type of sorption system (oil and oil/water) were evaluated by experimental planning. The fiber obtained was characterized by Fourier transform infrared spectroscopy (FTIR), field-emission scanning electron microscopy (SEM-FEG), thermogravimetric analysis (TG/DTG), contact angle, and wettability. The fiber treated by combining NaOH and heat treatment (CPNaOHT) exhibited a large structure with an internal diameter of 42.99 ± 3.98 μm, roughness, and hydrophobicity on the surface with a contact angle of 101 ± 2°. The sorption capacity of oil ranged from 190.32 g/g to 98.9 g/g. After five cycles of recycling, the fiber still maintains about 70% of its initial sorption capacity and presented low liquid desorption (0.25 g). In this way, it can be used as an efficient sorbent to clean up spills of oil and oil products.