The aim of this study was to investigate a potential biorefinery process to realize the high utilization of Camellia oleifera shell (COS), which is an agricultural by-product mainly composed of cellulose, hemicellulose, and lignin. Before treatment by steam explosion, the COS was impregnated with water, 3.0 wt% NaOH solution, or 3.0 wt% H2SO4 solution. The morphological structure and chemical composition of the steam-exploded COS pulp were investigated. The results indicated that the impregnation treatments increased the cellulose content of the steam-exploded COS pulp and decreased the hemicellulose and lignin content. The morphology of steam-exploded COS fiber was short, coarse and stiff. Hydrophobic and colorful handsheets were fabricated by mixing proportional bleached softwood fiber. This study demonstrated that COS was a potential material for the papermaking industry, and the combination of water impregnation and steam explosion treatment for COS was a good pulp process.