Poly(aryl imino sulphone)s (PAIS) as novel high-performance polymers have been obtained by the condensation polymerization of 4,4'-dibromodiphenyl solfone with different primary aromatic diamines via Palladium-catalyzed aryl amination reaction. 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 (DSC) and thermal analysis (TG) measurements showed that polymers possessed high glass transition temperature (Tg>145°C) and good thermal stability with high decomposition temperatures (TD>450°C). These novel polymers also exhibited good mechanical behaviors and good solubility.