Today, the applications of natural polysaccharide-based nanofibers are growing in drug delivery and food industries. They also showed their capability as packaging due to biodegradability, mechanical strength, barrier properties, thermal stability, antioxidant, and antimicrobial features. Natural polysaccharides come from different sources, such as plants, microbes, and animals. Natural polysaccharide-based nanofibers can be considered sustainable packaging in contrast to plastic packaging due to their safety and biodegradability. Smart packaging is a new trend in packaging materials, and natural polysaccharides can be applied as smart packaging. They can work as an indicator that confirms food health in food packaging. Electrospinning is one of the most used methods for the fabrication of nanofibers, and it can also be used for the fabrication of natural polysaccharide nanofibers. This method can be scaled up and used to fabricate nanofibers on a large scale. This paper will review recent studies on natural polysaccharide-based nanofiber as packaging materials and their benefits. We also discuss the challenges and limitations of their scale-up and electrospinning process. Furthermore, we will discuss the future perspective of natural polysaccharide-based nanofiber as a new sustainable packaging.