AbstractPhotocatalyst‐enzyme coupled system for harnessing solar light stands out as a highly promising avenue that facilitates bio‐transformation and produces solar fuels. This study explores the integration of a metal‐free photocatalyst in the bio‐reduction of furfural to produce furfuryl alcohol. However, the bio‐reduction of furfural to produce furfuryl alcohol faces challenges due to harsh reaction conditions and expensive catalysts. Likewise, photocatalysts confront various research obstacles, including the absence of long‐lasting photogenerated charge carriers (electrons and holes), stability, and reusability. This work introduces an eco‐friendly and benign catalytic system, featuring an easily prepared photocatalyst using TBA (2,4,6‐tribromo aniline) by standard Ullman coupling. The newly designed polymeric tribromo aniline (PTBA) is cost‐effective, with outstanding light harvesting characteristics, appropriate energy band gap, and remarkably enhanced ability for transfer and migration of photo‐generated carriers. The research aims to optimize parameters for efficient conversion of furfural to produce furfuryl alcohol and also the photocatalytic production of NADH (80.08 %) from consumed NAD+. The photocatalytic efficiency was estimated by the yield percentage of this organic transformation. The absence of metals in the photocatalyst enhances sustainability, showcasing its potential in the green synthesis of furfuryl alcohol which is a valuable chemical with diverse applications.