Nanoscale fibers and non-woven meshes composed of DNA complexed with a cationic surfactant (cetyltrimethylammonium chloride, or CTMA) have been fabricated through electrospinning. The DNA-CTMA complex can be electrospun far more easily than DNA alone. Incorporation of a hemicyanine chromophore resulted in materials that demonstrated amplified emission as compared to thin films of identical composition. The enhanced fluorescence resulted from both the fiber morphology (5-6- fold amplification) and specific interactions (groove-binding) between the chromophore and DNA (18-21-fold amplification). The mechanical properties of freestanding electrospun non-woven fiber meshes were evaluated, and revealed stress-induced alignment of DNA strands within the DNA-CTMA fibers. These fiber-based materials are easily processable into a variety of morphologies, and have promise for applications in molecular electronics, filtration, sensors, and the medical industry.