Aloe vera (A. barbadensis Miller) is probably one of the most popular plants, widely studied because of numerous properties associated with the polysaccharides present in its gel. In particular, two main types of bioactive polysaccharides can be distinguished in the A. vera gel: an acetylated mannose-rich polymer that functions as storage polysaccharide, and a galacturonic acid-rich polymer as the main component comprising the cell walls of the parenchymatous tissue. Interestingly, most of the beneficial properties related to the aloe plant have been associated with the acetylated mannose-rich polysaccharide, also known as acemannan. However, the composition and structural features of these polysaccharides, as well as the beneficial properties associated with them, may be altered by different factors, such as the climate, soil, postharvest treatments, and processing. Further, different analytical methods have been used not only to identify but also to characterize the main polysaccharides found in parenchyma of A. vera leaf. Within this context, the main aim of this review is to summarize the most relevant information about the structural and compositional features of the main polysaccharides found in the A. vera gel as well as the most relevant analytical techniques used for their identification and their influence on the technological, functional, and beneficial properties related to the A. vera plant.