Livingcationicpolymerization reactions using organotellurium compounds as initiators are reported. Polymerization of vinylethers in the presence of an organotellurium initiator and a Lewis acid, such as In(OTf)3 and BF3⋅OEt2, affords well‐controlled poly(vinylether)s with predetermined molecular weights and narrow molecular‐weight distributions. Poly(meth)acrylates possessing organotellurium group