A method of measuring the temperature of molten iron by immersing a front end portion of a thermocouple temperature sensor into the molten iron, the thermocouple temperature sensor involving a platinum-rhodium-based thermocouple having first and second metal wires, a connection point of the metal wires forming a heat sensing portion, an oxide insulation tube accommodating the metal wires, the heat sensing portion of the thermocouple being exposed from a front end portion of the insulation tube, a noble-metal cap mainly composed of platinum group metal completely covering the front end portion of the insulation tube to thereby cover the heat sensing portion of the thermocouple, an inner protecting tube mainly composed of platinum group metal completely covering the front end portion of the insulation tube to thereby cover the heat sensing portion of the thermocouple, an inner protecting tube mainly composed of alumina accommodating the insulation tube and the noble-metal cap, and a protecting tube made of metal-boride-based ceramics accommodating the inner protecting tube.