Poly(aryl imino sulfone)s (PAISs) as novel high-performance polymers have been obtained by the condensation polymerization of 4,4'-dibromodiphenyl sulfone with different primary aromatic diamines via Palladium-catalyzed aryl amination reaction. The influence of the halogen-containing monomers, solvent, concentration, and temperature on the polycondensation reaction was investigated. The structure of polymers synthesized was characterized by means of FT-IR, NMR spectroscopy, and elemental analysis, the results showed an agreement with the proposed structure. Differential scanning calorimetry and thermal analysis measurements showed that polymers possessed high glass transition temperature (T-g > 145 A degrees C) and good thermal stability with high decomposition temperatures (T-D > 450 A degrees C). These novel polymers also exhibited good mechanical behaviors and good solubility.