The chemical composition, anatomical characteristics, lignin distribution, and cell wall structure of oil palm frond (OPF), coconut (COIR), pine-apple leaf (PALF), and banana stem (BS) fibers were analyzed. The chemical composition of fiber was analyzed according to TAPPI Methods. Light microscopy (LM) and transmission electron microscopy (TEM) were used to observe and determine the cell wall structure and lignin distribution of various agro-waste fibers. The results revealed differences in anatomical characteristics, lignin distributions, and cell wall structure of the different types of fibers investigated. Nevertheless, transmission electron microscopy (TEM) micrographs have confirmed that the well wall structure, in each case, could be described in terms of a classical cell wall structure, consisting of primary (P) and secondary (S 1 , S 2 , and S 3 ) layers.