PS-PEO diblock copolymers form micelles in an aqueous solution. The properties of the micellar solution such as aggregation number and second virial coefficient can be markedly changed due to the solubilization of a second solvent. Second solvent means, in this context, a solvent compatible with the core block copolymer. Tetrahydrofuran (THF) and toluene were chosen as the second solvent since toluene and THF are good solvents for both PS and PEO. However, THF is miscible with water, while toluene is only sparingly soluble. Laser light scattering measurement was used to study and compare the effects of these two second solvents on the formation of micelles. Furthermore, two kinds of copolymer, which have different block lengths of PS but the same total molecular weight of the diblock copolymers, are also studied. In all instances, only a slight amount of a second solvent was added. Our results show that the degree of aggregation, micelle interaction strength, and structure are strongly dependent on both the concentration and type of the second solvent. The primary reason is due to absorption of second solvent into the core.