Scramjet engines with their very high specific impulse have the potential to outperform rocket motors as a means of propelling hypersonic vehicles. The scope of this project is to determine temperatures in the scramjet combustor using an advanced optical diagnostic technique, namely laser-induced fluorescence. Presently, direct temperature measurements are not readily available for scramjets, due to three reasons. Firstly, commonly-used gauges for temperature measurements, such as thermocouples and heat transfer gauges would not survive or would be damaged at the extreme temperatures typically occurring in scramjets (around T = 1100 -2500 K), and therefore these gauges would not give accurate readings. Secondly, measurements with any gauges would be intrusive, and their presence in the flow might cause large disturbances. Thirdly, these gauges can only provide discrete, point measurements. Laser-induced fluorescence measurements present an optical non-intrusive technique to resolve temperatures in the combustor. Additionally, LIF measurements allow the temperatures in the combustor to be resolved at a higher spatial resolution than regular gauges. The new contribution made by this PhD project is the application of a sophisticated optical diagnostic technique, thermally-assisted laserinduced fluorescence, to the temperature measurements in the combustor of a supersonic combustion engine. The issues with the technique and the way it should be used for application to scramjet flows were explored. This required the development of the new knowledge and understanding of the spectroscopy that underpins the technique. The project is significant because, to the author's knowledge, this is the first time thermally-assisted LIF has been used for scramjet flows in a test facility. Currently available thermometry methods usually require averaged repeated experiments, thus causing high cost of experiments. This study represents successful single-shot scramjet temperature measurements. The project was approached theoretically (synthetic spectra), experimentally and numerically (CFD and LIF modelling).Radiation simulation programs providing synthetic OH spectra represent the theoretical part of this study, as they employ theoretical expressions for spectral calculations. The OH radical is an intermediate species in the combustion, created in high quantities, therefore allowing direct fluorescence measurements. In this work, three numerical codes were used -LIFBASE, SPARTAN and Photaura. SPARTAN and Photaura were modified in order to include the OH molecule. The results presented here show that OH spectra produced using these programs show very good agreement. All three programs give correct and reliable representation of the physical phenomena in the wavelength range studied.Experimental data was obtained through laser-induced fluorescence with a laser beam focused into the combustor exciting an OH molecule transition. The experiments were conducted in the T4 shock tunnel using a scramjet model. LIF measurements were performed t...