Light management in a photovoltaic device is much about efficient light harvesting by increasing internal reflection and absorption. Structured architectures aids in enhancing internal reflection hence higher light absorption. Various techniques have been employed to fabricate these structures. In this work, organic photoactive materials were electrosprayed, utilizing a high voltage electric field to charge a droplet suspended through a nozzle, at various solution concentrations. Various process parameters like applied voltage, flow rate, tip to collector distance were optimized to obtain hierarchical structures. Morphological and optical properties of these optimized structures were analyzed to get interesting pattern with enhancement in surface area and light absorption. These structures were further evaluated in photovoltaic device architecture.