Cellulose derived from cotton was ball-milled with some hydrophilic and hydrophobic solvents such as water, toluene, 1-butanol and also without solvent (dry state), and effect of the solvents on morphological and structural changes of the cellulose were investigated. The original fibrous cellulose was changed to the aggregated globular particles by water and dry state ball-milling, plate-like particles by toluene processing, and a mixture of rugged globular particles and plate-like particles by 1-butanol processing. The globular particles prepared without solvent showed fairly low crystallinity and their inter- and intra-molecular hydrogen bonds were deformed, leading to an increase in free hydroxyl groups. The globular particles prepared with water exhibited a mixture of crystalline structure as cellulose I, cellulose II and non-crystalline state. In the case of the products with toluene, the plate-like particles significantly retained their original crystalline structure and hydrogen bonds. The 1-butanol processing seems to give the particles consisting of cellulose I and small amounts of either non-crystalline or cellulose II. The cellulose/dye stuff mixtures under the presence of the above solvents were prepared using 4-aminoazobenzene to investigate the differences in the surface property of the particles prepared by the ball-milling processing. Characteristic color development of each cellulose particles was clearly distinguished depending on the effect of the solvent (cinnabar; without solvent, yellow; toluene and yellowish-green; water or 1-butanol).