4,4’-Di(benzimidazolyl)benzene sulfone, as the monomer, is very readily available by the reaction of 4,4’-dicarboxydiphenyl sulfone with o-phenylenediamine, and poly(arylene benzimidazole) sulfone (PABIS) has been synthesized by the condensation polymerization of bis(4-fluorophenyl) sulfone with di(benzimidazolyl)benzene sulfone via an N–C coupling reaction. The structure of the polymer was characterized by Fourier transform IR spectroscopy, 1H NMRspectroscopy and elemental analysis, and the results showed agreementwith the proposed structure. DSC and thermogravimetricmeasurements showed that PABIS possesses a high glass transition temperature (Tg =321 ?C) and good thermal stability with high decomposition temperature (Td >530 ?C). Additionally, PABIS exhibits good solubility in most polar organic solvents. Based on the good chemical and physical properties, hollow PABIS microspheres with diameters in the range 0.3–1.8mm were prepared by the micro-liquid technique and the double-layer latex technique. A new double T-channel droplet generator was developed for continuous fabrication of controlled-size hollow PABIS microspheres. The structures of the hollow PABIS microspheres were characterized, and they possessed equal wall thickness and good spherical symmetry.