The effect of main chain structure of anion-containing copolyesters on the properties of copolyester sizing agents was investigated. The copolyesters were prepared by conventional two step polymerization technique from DMT, DMI, DMS, EG, and DEG. The copolyesters synthesized were characterized by atomic absorption spectroscopy, $^1$H-NMR Spectroscopy, GC, FTIR Spectroscopy, and DSC. The solubility decreased as the DMT content increased. The copolyesters having DMT:DMI = 1:1 showed the minimum viscosity. The effect of EG content on the solution stability was not clear and the samples having high DMI content showed better solution stability. The water resistance was best when only DMI and EG were used, while it was worst when DMT:DMI was 1:0.