This article deals with the aspects of interfacial and surface characterization of natural fibers and their composites. Vegetable fibers and their composites have attracted the attention of scientists worldwide because of their favorable properties. The different chemical modifications of natural fibers and characterization aspects have been discussed. The adhesion between fiber and matrix is a major factor in determining the response of the interface and its integrity under stress. Therefore characterization of the interface is of utmost importance. Both fiber surface and polymer matrix surface can be modified to obtain a strong interface. Various treatments being used for the lignocellulosic surfaces and the characterization techniques have been illustrated. The four main techniques of interfacial characterization that are enumerated in this article are the micromechanical techniques, spectroscopic, microscopic and swelling techniques. The micromechanical techniques like fiber pull-out and fragmentation have been dealt with giving emphasis to experimental aspects. Recent studies dealing with interfacial study of different lignocellulosic fiber reinforced composites have also been cited.