The critical climate change and pollution have led scientists to research natural material. In the field of composites, natural fibers have started to replace synthetic fibers owing to their biodegradability, easy availability, good specific properties, etc. All research related to materials requires their characterization, whether it is the characterization of physical, chemical, or mechanical properties, spectroscopic techniques are of tremendous use, especially in natural composites where the natural fibers itself are made of complex carbohydrates, characterization of their properties is of utmost importance. The manufacturing of composite leads to many significant changes in their morphology, physical bonding, chemical bonding, etc., which is why it is important to observe these changes, which will directly affect the chemical, mechanical, and thermal properties. These changes can be easily identified with spectroscopic techniques. Moreover, the check for certain properties such as mechanical properties and tribological properties involves damage or breaking of material. By investigating the fracture, one can identify the fracture or wear phenomenon. For the study of all aforementioned phenomena, spectroscopy comes in very handy. This chapter deals with the study of epoxy/natural fiber composites using various phenomena like bonding, fracture, wear, etc. with the help of spectroscopic techniques.