Yucca fiber is a natural cellulose fiber that can be extracted from the Yucca plant leaves by retting. The physical properties of the Yucca fiber are extremely sensitive to the retting conditions. This research was designed to study the effects of chemical retting on the structural and properties of this fiber. Chemical retting was done by soaking the Yucca leaf in 10 to 150 g/l sodium hydroxide concentration at 80 to 100 °C for 60 to 240 min. Fiber characteristics such as fineness, tenacity, functional groups, crystallinity, thermal degradation, and surface morphology were then investigated. The Yucca fibers exhibited high crystallinity (56–66%), high tenacity (36–46 cN/tex), and low linear density (3–5 tex). It was also found that the elementary fiber had a mean diameter of about 1.2 µm and a helical structure of square-shaped spires. The thermogravimetric analysis also indicated that the Yucca fiber had the thermal stability of up to 250 °C. Based on the findings, the Yucca fiber may be suitable for various applications such as a reinforcement material in the composites applications and can be turned to yarn for textile applications.