Polysaccharides synthesized by microorganisms (bacterial cellulose, dextran, pullulan, xanthan, etc.) have a set of valuable properties, such as being antioxidants, detoxifying, structuring, being biodegradable, etc., which makes them suitable for a variety of applications. Biocatalysts are the key substances used in producing such polysaccharides; therefore, modern research is focused on the composition and properties of biocatalysts. Biocatalysts determine the possible range of renewable raw materials which can be used as substrates for such synthesis, as well as the biochemistry of the process and the rate of molecular transformations. New biocatalysts are being developed for participating in a widening range of stages of raw material processing. The functioning of biocatalysts can be optimized using the following main approaches of synthetic biology: the use of recombinant biocatalysts, the creation of artificial consortia, the combination of nano- and microbiocatalysts, and their immobilization. New biocatalysts can help expand the variety of the polysaccharides’ useful properties. This review presents recent results and achievements in this field of biocatalysis.