We explored for the first time the ability of a three-dimensional polyacrylonitrile/ZnO material-prepared by a combination of electrospinning and atomic layer deposition (ALD) as a new material with a large surface area-to enhance the performance of optical sensors for volatile organic compound (VOC) detection. The photoluminescence (PL) peak intensity of these one-dimensional nanostructures has been enhanced by a factor of 2000 compared to a flat Si substrate. In addition, a phase transition of the ZnO ALD coating from amorphous to crystalline has been observed due to the properties of a polyacrylonitrile nanofiber template: surface strain, roughness, and an increased number of nucleation sites in comparison with a flat Si substrate. The greatly improved PL performance of these nanostructured surfaces could produce exciting materials for implantation in VOC optical sensor applications.