Naturally-derived biopolymers such as alginate, chitosan, cellulose, agarose, guar gum/guaran, agar, carrageenan, gelatin, dextran, xanthan, and pectins, etc. have appealed significant attention over the past several years owing to their natural abundance and availability all over the years, around the globe. In addition, their versatile properties such as non-toxicity, biocompatibility, biodegradability, flexibility, renewability, and the availability of numerous reactive sites offer significant functionalities with multipurpose applications. At present, intensive research efforts have been focused on engineering enzymes using natural biopolymers as novel support/composite materials for diverse applications in biomedical, environmental, pharmaceutical, food and biofuel/energy sectors. Immobilization appears as a straightforward and promising approach to developing biocatalysts with improved catalytic properties as compared to their free counterparts. Biopolymers-assisted enzymes are more stable, robust, and recoverable than that of free forms, and can be employed for continuous biocatalytic reactions. The present review highlights the recent developments and use of biopolymers and their advanced composites as support carriers for the immobilization of a variety of different enzymes to develop biocatalysts with desired catalytic activity and stability characteristics for emerging applications.