Novel cellobiose and cellulose (DP n =ca. 30) derivatives, (14) carrying a pyrene group as a single fluorescent probe at the reducing end, were prepared in order to investigate their self-assembly systems in solutions. The relative intensity of the excimer emission at ca. 480 nm due to dimerized pyrenes (intensity I E ) to the monomer emission at ca. 380 nm due to isolated pyrene (intensity I M ), i.e., I E /I M , was monitored in various solutions. In water/dimethyl sulfoxide (DMSO) mixed solvent (0 -98%, v/v), the ratio I E /I M remained low (0.04) for compound 6 over the range of water concentrations, indicating that pyrenes at C-1 position of compound 6 were diffused. On the other hand, the ratio I E /I M increased (0.04 -4.96) for compound 7 with the increase in water concentration, indicating that pyrenes at C-1 position were associated. In aqueous NaOH solutions (4.4 -17.5%, w/w), compound 14 showed a large increase in the ratio I E /I M (0.84 -8.14) with the increase in NaOH concentration, compared to compound 13 (0.06 -0.41). It was found that the association of hydrophobic groups at the reducing-end of cellulose could be controlled by the hydrophilic -hydrophobic balance of compounds and the solvent polarity.