By using a simple model to relate the electromotive force drift rate of Pt–Rh thermoelements to dS/dc, i.e. the sensitivity of the Seebeck coefficient, S, to rhodium mass fraction, c, the composition of the optimal pair of Pt–Rh wires that minimizes thermoelectric drift can be determined. The model has been applied to four multi-wire thermocouples each comprising 5 or 7 Pt–Rh wires of different composition. Two thermocouples were exposed to a temperature of around 1324 °C, one thermocouple to around 1492 °C, i.e. the melting points of the Co–C and Pd–C high temperature fixed points, respectively, and one thermocouple to a series of temperatures between 1315 °C and 1450 °C. The duration of exposure at each temperature was several thousand hours. By performing repeated calibrations in situ with the appropriate fixed point during the high temperature exposure, the drift performance has been quantified with high accuracy, entirely free from errors associated with thermoelectric homogeneity. By combining these results it is concluded that the Pt-40%Rh versus Pt-6%Rh is the most stable at the temperatures investigated. A preliminary reference function was determined and is presented.