Heated wires in a special symmetrical arrangement were used for electrochemical experiments in a thin, hot, near-electrode solution layer. By application of a series of short-time heat pulsing sequences with current sampling and synchronized polarization steps, voltammetric curves above the boiling point were recorded. Methods for determining and controlling the actual temperature are presented. The temperature dependence of quantities such as diffusion coefficient or electrode potential can be determined in a convenient manner. Examples are given for different redox systems, including hexacyanoferrate(III)–(II), Fe³⁺–Fe²⁺, bromate, oxalic acid and formaldehyde.