Polyimide (PI) offers promising features such as high strength and excellent thermal stability for flexible solar panels. The flexible solar cell demands maximum absorption of solar insolation through stacked layers to enhance its performance. However, the fluorescence emission (FE) in inactive polyimide substrate hinders the absorption of irradiated solar energy. In this research work, an attempt has been made to generate rippled morphology on PI substrate using laser processing that enhances the absorption and moderates the FE. These changes are confirmed by calculating the Urbach energy (Eu) of the rippled structure, which is found to be 2.5 times that of the pristine substrate. Furthermore, to reduce the FE, tungsten (W) was coated on the rippled structure of the laser-processed PI, and a significant reduction of 70% FE is achieved compared to the FE of unprocessed PI. These enhanced characteristics of PI obtained by laser processing will be highly helpful for improving the overall performance of flexible solar cells.