Morphology of polyester fiber was physically modified by solvent treatment. PET fiber was treated with N,N-dimethylformamide (DMF) at 100, 120, $140^{circ}C$ for 10 minutes without tension. The structural changes in the morphology of DMF-induced modified PET fiber were FTIR and SEM analysis. Also dyeing behavior of DMF-treated polyester fibers with various disperse dyes was studied to detect changes of amorphous area in fine structure. DMF treatment resulted in increases in total void content, degree of crystallinity, trans isomer content, chain folding, segmental mobility and molecular packing, but it resulted in decreases in amorphous orientation, intermolecular forces and individual void size through longitudinal shrinkage, lateral welling and removal of oligomers. Void-size distribution could be estimated from the dye uptake with various sizes of disperse dyes. In contrast to the large increases in dye uptake with small dye molecules, there is no and little dye uptake with the bulkiest dye, which means that void size is bigger or smaller than the volume of each dye. Diffusion rates of dye molecules showed increases. This dyeing study revealed that the disperse dyeing is very effective method for characterizing the internal morphology of polyester fiber.