The invention discloses a preparation method of high-electromagnetic-shielding-effectiveness full-biomass-based carbon aerogel. The required raw materials comprise cellulose. The method comprises thefollowing steps of raw material drying, preparation of a cellulose solution, preparation of cellulose aerogel and preparation of carbon aerogel. According to the method, celluloses is used as a precursor, through dissolution regeneration, cosolvent treatment and freezing drying, a three-dimensional continuous opening sheet layered grid structure of the cellulose aerogel is regulated and controlled, the stable and excellent electric conduction network (592.3 S/m) is constructed through high-temperature carbonization, and the efficient electromagnetic shielding performance (106.3 dB) of the carbon aerogel is achieved. The carbon aerogel has a wide precursor source and is environmentally friendly, a solvent system is nontoxic and low in price, the material preparation process is simple, the technology is easy to control, the production cost is low, and the carbon aerogel has high potential of large-scale production.