The usage of new cellulosic fibers in industrial applications is massive because of its excellent performances. These fibers are utilized especially for manufacture of high-performance composites. Coconut leaf sheath (CLS) fibers are extracted for leaf sheath of coconut tree. The aim of this paper is to study the possibility of using a natural fiber CLS as an alternative for polymer composites. In the current study, the consequence of NaOH treatment on structural, thermal and morphological behavior of treated and untreated coconut leaf sheath (CLS) fiber in terms of single fiber tensile strength, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (×RD), thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) has been explored. From SEM analysis, it was identified globular lumps spread consistently over the fiber which could help the mechanical interlock with the resin. The outcomes from the experimentation exposed that the NaOH treatment has impacted in the eradication of amorphous hemicellulose and lignin contents from the CLS fiber surface and in turn resulted in excellent structural and thermal stability behaviour of fiber. The present work endorses the great potential of CLS fibers to be utilized for bio-reinforcement in order to fabricate lightweight composite structures, employed in automobile and structural applications.