The issues related to determining the nonsinusoidal voltage coefficients at large industrial enterprises of non-ferrous metallurgy with a high specific weight of non-linear loads containing higher harmonics voltage components require special attention. The questions concerning development of an experimental research technique of amplitude-frequency characteristics of the higher voltage harmonics in power supply systems of industrial enterprises of non-ferrous metallurgy are considered in the article. A rank analysis of the higher voltage harmonics of Noah's caste spectrum has been conducted. This analysis shows that correlation coefficients between nonsinusoidal coefficients of the Noah's share and pointer caste shares of energy consumers for non-ferrous metallurgy enterprises are 0.56 and 0.37, respectively. Further research of non-sinusoidal voltage in power supply systems of industrial enterprises is highly recommended.