Bacterial cellulose is an attractive biopolymer for a number of applications including food, biomedical, cosmetics, and engineering fields. In addition to renewability and biodegradability, its unique structure and properties such as chemical purity, nanoscale fibrous 3D network, high water-holding capacity, high degree of polymerization, high crystallinity index, light transparency, biocompatibility, and mechanical features offer several advantages when it is used as native polymer or in composite materials. Structure and properties play a functional role in both the biofilm life cycle and biotechnological applications. Among all the cellulose-producing bacteria, acetic acid bacteria of the Komagataeibacter xylinus species play the most important role because they are considered the highest producers. Bacterial cellulose from acetic acid bacteria is widely investigated as native and modified biopolymer in functionalized materials, as well as in terms of differences arising from the static or submerged production system. In this paper, the huge amount of knowledge on basic and applied aspects of bacterial cellulose is reviewed to the aim to provide a comprehensive viewpoint on the intriguing interplay between the biological machinery of synthesis, the native structure, and the factors determining its nanostructure and applications. Since in acetic acid bacteria biofilm and cellulose production are two main phenotypes with industrial impact, new insights into biofilm production are provided.