Accurate measurements of combustion gas temperature and the coefficient of heat transfer between the gas and the combustion chamber wall of internal combustion engine in cyclic operations are difficult at present. Hence the only method available for determination of states of thermal load and heat loss to the combustion chamber wall in a cycle is to measure the instantaneous temperature on the combustion chamber wall surface accurately and precisely using proper thin-film thermocouples, then to calculate the instantanenous heat flux flowing into the wall surface by means of numerical analysis. However, it is necessary to pay adequate attention to the effects of thermophysical properties of the thermocouple materials on the measured values, since any thermocouple consists of several kinds of materials which are different from those of portions to be measured. This paper describes findings obtained through the studies made on structures of thermocouples developed by the authors et al. aiming at accurate determinations of instantanenous heat flux flowing into metallic and ceramic combustion chamber walls, together with the results of the applications to actual engine operations.