The straightforward synthesis of a series of poly(thioether)s by photoinduced thiol-ene click polyaddition of ,-alkylene thiols is reported. It is found that linear and telechelic poly(thioether)s can be directly obtained from ,-alkylene thiols with, for example, alkyl chain length of m = 1,2,3, and 9. The reaction proceeds without additives such as (radical) initiators or metal compounds and can simply be carried out by UV-irradiation of the bulk monomer or monomer solution. Ex situ kinetic studies reveal that the reaction proceeds by a typical a step-growth polyaddition mechanism. As the homologue series of poly(thioether)s are now synthetically accessible, new direct pathways to tailored poly(alkyl sulphoxide)s and poly(alkyl sulfone)s are now possible.