The quest for efficient and sustainable methods to mitigate Carbon Dioxide (CO2) emissions is a pressing global challenge. This study delves into the crucial role of polymers in tailoring the performance of Titanium Dioxide (TiO2) nanofibers for CO2 conversion reactions. By systematically comparing the influence of different polymers, specifically Polyvinyl Pyrrolidone (PVP) and Polyvinylidene Fluoride (PVDF), on the CO2 conversion activity of TiO2-NFs, we shed light on the remarkable potential of polymeric selection to fine-tune catalyst properties. The paper uses advanced experimental techniques to analyze the structural and morphological properties of PVP-TiO2-NFs and PVDF- TiO2-NFs demonstrating their various morphologies. The investigation involves SEM, TEM, XRD, BET and UV-Vis spectroscopy to better understand the charge separation and recombination processes involved in both materials' CO2 conversion. The results show considerable differences, choice of polymer significantly impacts the CO2 conversion performance of TiO2-NFs. PVP based NFs exhibit enhanced surface area and porosity, resulting in superior catalytic activity, while PVDF based NFs demonstrate remarkable stability. These findings pave the way for innovative approaches to tackle climate change and develop a more environmentally friendly future by advancing energy-efficient and long-lasting photocatalytic technology.