Cellulose, the most abundant biopolymer, is the key to the sustainable material revolution. The circular economy approach and green chemistry principles have enabled new routes to material design by creating physically or chemically crosslinked biopolymer networks. The present review aims to overview cellulose's synergetic interactions with various biopolymers like lignin, hemicellulose, pectin, starch, alginate, chitin, chitosan, collagen, silk, etc., and the various functionalizations achieved in the resulting materials. Synergetic interactions are presented as obtained properties, material development routes, applications, and sustainable alternatives to existing high-performance materials. By reviewing the most recent advances in understanding biopolymer properties, structure, and functionality, an in-depth approach to designing biopolymer-based materials is presented. A section of the review is dedicated to 3D printing as a means to achieve rapid development of these versatile and advanced materials. Biopolymers, as renewable and abundant resources, can be transformed into value-added components through extraction from various crops, industrial processing and forestry wastes, or animal byproducts.