Organotellurium compounds-mediated living radical polymerization (TERP) is one of the most robust tools of living free radical polymerizations (LRP). However, synthesis and purification of organotellurium compounds are time-consuming and to be operated in an inert atmosphere due to their extreme sensitivity to trace oxygen. In this article, a simple process of TERP, operating in open air, has been reported. It has demonstrated that the crude organotellurium compound, ethyl 2-phenyltellanyl-2-methylpropionate, could mediate 2,2'-azobis (isobutyronitrile) initiated styrene (St) and butyl acrylate (BA) polymerization as an LRP system. For the bulk and solution polymerization of St and the solution polymerization of BA, the molecular weights of produced polymers increased linearly with the monomer conversions. During the same time, the molecular weight distributions kept under 1.3. The UV-vis spectrum showed that the PS polymer chain bearing C-TePh end group. With the sequential monomer addition technique, a clean diblock polymer of PS-b-PBA was also obtained.