Polyhydroxy butyrate-co-valerate (PHBV) - Zinc oxide (ZnO) nano composite fibers were prepared using electrospinning. The structural and optical properties were studied using Fourier transform infrared spectroscopy (FT-ER), X-ray diffraction (XRD) and photoluminescence study (PL). The morphology observed with scanning electron microscope (SEM) revealed no significant changes in the nano composite fibers as compared to bare polymer. The low concentration of ZnO nanoparticles resulted in an increase in overall crystallinity of the polymer matrix which was confirmed from FT-IR and XRD results. The photoluminescence (PL) study indicated the quenching of visible emission in the composite fibers. The ratio of UV to visible emission (I-uv/I-vis) intensity was found to be 12.8 times enhanced in the composite fibers compared to bare ZnO nanoparticles. The nanofibrous mats are self supported and hence offer potential applications in optoelectronic devices and the biomedical imaging.