Petroleum-based synthetic plastics play an important role in our life. As the detrimental health and environmental effects of synthetic plastics continue to increase, the renewable, degradable and recyclable properties of cellulose make subsequent products the “preferred environmentally friendly” alternatives, with a small carbon footprint. Despite the fact that the bioplastic industry is growing rapidly with many innovative discoveries, cellulose-based bioproducts in their natural state face challenges in replacing synthetic plastics. These challenges include scalability issues, high cost of production, and most importantly, limited functionality of cellulosic materials. However, in order for cellulosic materials to be able to compete with synthetic plastics, they must possess properties adequate for the end use and meet performance expectations. In this regard, surface modification of pre-made cellulosic materials preserves the chemical profile of cellulose, its mechanical properties, and biodegradability, while diversifying its possible applications. The review covers numerous techniques for surface functionalization of materials prepared from cellulose such as plasma treatment, surface grafting (including RDRP methods), and chemical vapor and atomic layer deposition techniques. The review also highlights purposeful development of new cellulosic architectures and their utilization, with a specific focus on cellulosic hydrogels, aerogels, beads, membranes, and nanomaterials. The judicious choice of material architecture combined with a specific surface functionalization method will allow us to take full advantage of the polymer’s biocompatibility and biodegradability and improve existing and target novel applications of cellulose, such as proteins and antibodies immobilization, enantiomers separation, and composites preparation.