End‐of‐life paper products, including food packages and rejected fibers from the paper industry, are unrecyclable biomass wastes and thus generally landfilled or incinerated. One of the major obstacles to their recycling is the existence of impurities besides cellulose fiber in the biomass wastes. In this study, a fabrication method is investigated to upcycle biomass wastes directly into high‐performance aerogels without separation of impurities. Surprisingly, this study observes that residual impurities participate in cross‐linking reactions for the aerogel formation. In this study, zinc chloride salt hydrate is applied to convert biomass wastes to aerogel via a dissolution‐regeneration process. The fabricated aerogels exhibited high water absorption capacity (15 times its weight), as well as comparable mechanical strength and thermal insulation performance to the reported cellulose aerogels. In addition, the impurities (i.e., calcium‐based inorganic salt) assisted in the cross‐linking of the cellulose network for the aerogel formation. The scanning electron microscopy (SEM) image of the aerogel generated from the rejected fibers showed a honeycomb inner structure. The rejected fiber aerogels also demonstrated a high compressive modulus of 51 MPa and a low thermal conductivity of 0.029 W m−1 K−1. The results for water absorption and thermal insulation suggest excellent potential across various application domains.