Increasingly, the world is realizing that better use must be made of precious natural resources. Today, with the enrichment of people's awareness on environment problems and the demand of environment-friendly fabric, natural fibers have received a great deal of attention due to their great importance of "green" and health protection properties and have been widely used in many fields, such as textile industry and daily life. Traditional resource of four natural fibers, cotton, wool, silk, and flax is after all limited. So, many new plant fibers, such as hemp, apocynum, mulberry bast fiber, pineapple leaf fiber, banana fiber, bamboo fiber, kapok fiber, and so on, have been exploited in recent years. The luxury sector, particularly fashion has a high environmental footprint and is responsible for a significant amount of waste. Designers committed to sustainable processes face a severe lack of options in terms of the actual goods used to make their products, with everything from fabric to embellishments being in short and expensive supply. This chapter aims to give an insight into the comprehensive details of conventional as well as unconventional sustainable luxury fibers which are going to be dominated in luxury fashion industry in the forthcoming years.