Due to growing environmental consciousness and the depletion of oil supplies, numerous efforts have been made to replace synthetic fibers in fiber-reinforced composites with natural fibers (NFr). The low cost and abundance of NFr and its biodegradability and low density have encouraged researchers worldwide to study their potential applications in several industrial sectors. However, NFr has several disadvantages: excessive moisture absorption and subsequent swelling and degradation, low chemical and fire resistance, and insufficient interfacial interactions with polymers. Consequently, there is great interest in modifying the surface of NFr using a variety of methods. This chapter presents an overview of the NFr, its characterization, the problems associated with adding NFr to polymer composites. This literature survey suggests an in-depth review of photocatalysis by utilizing photocatalysts nanoparticle (PHNPs) aimed at increasing the hydrophobicity and interfacial bonding between the NFr and the matrix Using a photo-induced oxidation mechanism to disassemble water molecules, pollutants, and bacteria in a wet environment. Additionally, we reviewed the effects of these PHNPs on the moisture absorption, mechanical characteristics, and dimensional stability of NFr composites. As a result, this review article may make a valuable contribution to researchers interested in coating and treating NFr to further enhance their surface characteristics.