摘要： This study reports a step-growth click-polymerization of 1,4-benzenedimethane (BDMT) and diethylene glycol divinyl ether (DEGVE) with 4-(N,N-diphenylamino)-benzaldehyde (DPAB) as a photoredox catalyst under irradiation of visible light. DPAB exhibits a strong UV–vis absorption at 350 nm and a strong fluorescence emission at 480 nm in anisole. There is a strong fluorescence quenching between BDMT and DPAB. The molecular weight of the polythiolether can be controlled by reaction time and monomer feed ratios. More importantly, α,ω-dithiol and α,ω-divinyl telechelic polythiolether oligomers are successfully synthesized by simply changing the molar ratios of BDMT to DEGVE. 1H NMR and MALDI-TOF MS spectra demonstrate that the oligomers have high end group fidelity. In addition, strong fluorescence is observed when the α,ω-dithiol terminated polythiolether adds with N-(1-pyrenyl) maleimide, indicating that the as-prepared polythiolether bears reactive thiol end groups. Furthermore, high molecular weight polythiolether are prepared by chain extension with reactive polythiolether oligomers as macro-monomers. For example, α,ω-divinyl oligomer (Mn = 2000 g mol?1) could further react with α,ω-dithiol oligomer (Mn = 2400 g mol?1) to form high molecular weight polythiolether (Mn = 6000 g mol?1).