For the first time tellurium has been purified by means of plasma-enhanced chemical transport reaction with intermediate formation of tellurium hydride (H2Te) and the following its thermal decomposition with formation of high-purity tellurium and hydrogen. Recently developed direct interaction of hydrogen with tellurium vapors at low pressure in inductively coupled non-equilibrium plasma discharge underlain the novel approach of purification. The metal and carbon-containing impurities behavior was also studied. The possible mechanism of their conversion during the process has been discussed. In order to demonstrate effectiveness of the suggested method, As2Te3 films have been prepared from the initial tellurium and tellurium after purification. They were studied by mass-spectrometry technique for comparison.