A single-step synthesis of super-water-repellent oil sorbents based on cellulose acetate (CA) mats is reported in this paper. Key phenomenological mechanisms involving roughness and changes in chemistry are used to describe the change in hydrophobic behavior of the CA mats. Contact angle calculations followed by Cassie's model apparent contact angle prediction have shown roughness alone is not capable of producing the super-hydrophobicity exhibited by as-spun mats. Fourier transform infrared spectroscopy of spin coated and electrospun mats shows a significant difference in the stretching of the hydroxyl bonds of the two materials. As it is this hydroxyl group which adds to the overall polarity of surface thus hydrophilicity of the material, we propose that the electrospinning process not only creates a rougher surface but also alters the chemistry of the electrospun cellulose acetate mats which ultimately gives rise to the reported hydrophobicity. Finally, due to their water repellent nature, and oleophilicity of the as-spun mats were tested as oil sorbent mats. The as-spun mats were capable of absorbing thirty times their weight in oil demonstrating their application for oil-water remediation.