A hierarchy of nanostructured-ZnO was fabricated on the electrospun nanofibers by atomic layer deposition (ALD) and hydrothermal growth, subsequently. Firstly, we produced poly(acrylonitrile) (PAN) nanofibers via electrospinning, then ALD process provided a highly uniform and conformal coating of polycrystalline ZnO with a precise control on the thickness (50 nm). In the last step, this ZnO coating depicting dominant oxygen vacancies and significant grain boundaries was used as a seed on which single crystalline ZnO nanoneedles (average diameter and length of ∼25 nm and ∼600 nm, respectively) with high optical quality were hydrothermally grown. The detailed morphological and structural studies were performed on the resulting nanofibers, and the photocatalytic activity (PCA) was tested with reference to the degradation of methylene blue. The results of PCA were discussed in conjunction with photoluminescence response. The nanoneedle structures supported the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. The enhanced PCA, structural stability and reusability of the PAN/ZnO nanoneedles indicated that this hierarchical structure is a potential candidate for waste water treatment.