A Photonics device requires uniform periodic structural arrangement. Various techniques have been used to fabricate these types of structures, which employs several steps of fabrication. This work proposes single step hierarchical array of equal submicron size porous structure fabricated through tuning electrospinning processing parameters. The dictating parameters were high voltage, tip to collector distance and solvent used on the evolving structure. Morphological and optical investigations suggested the uniform periodic topography and enhancement in light absorption, which is assumed due to internal reflection of light. This structure was evaluated for better light harvesting as active layer in organic photovoltaic devices using poly (3 hexyl thiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) blend, and further studying enhancement in photoelectrical characteristics.