The development of state-of-the-art AlGaN/GaN high electron mobility transistors (HEMTs) has shown much promise for advancing future RF and microwave communication systems. These revolutionary devices demonstrate great potential and superior performance and many commercial companies have demonstrated excellent reliability results based on multiple temperature accelerated stress testing. However, a physical understanding of the various reliability limiting mechanisms is lacking and the role and relative contribution of the various intrinsic material factors, such as physical stress and strain has not been clearly explained in the literature. Part of issues that impact device reliability are the mechanical stresses induced in the devices as well as the self-heating that also limit device performance. Thus, quantification of stress and temperature in AlGaN/GaN HEMTs is of great importance. To address some of the needs for metrology to quantify stress in AlGaN/GaN HEMTs, micro-Raman spectroscopy and micro-photoluminescence (micro-PL) were utilized to quantify the residual stress in these devices. Through the use of micro-Raman and micro-PL optical characterization methods, mapping of the vertical and lateral stress distributions in the device channels was performed. Results show that stress can be influenced by the substrate material as well as patterned structures including metal electrodes and passivation layers. Previously developed and reported micro-Raman thermometry methods require an extensive calibration process for each device investigated. To improve the implementation of micro-Raman thermometry, a method was developed which offers both experimental simplicity and high accuracy in temperature results utilizing a universal calibration method that can be applied to a broad range of GaN based devices. This eliminates the need for performing calibration on different devices. By utilizing this technique, it was revealed that under identical power dissipation levels, the bias conditions (combination of Vgs and Vds) alter the heat generation profile across the conductive channel and thus influence the degree of device peak temperature. The role of stress in the degradation of AlGaN/GaN HEMTs was also explored. A combined analysis using micro-Raman spectroscopy, coupled electro-thermo-mechanical simulation, and electrical step stress tests was conducted to investigate the link between performance degradation and the evolution of total stress in devices. It was found that in addition to stresses arising from the inverse piezoelectric effect, the substrate induced residual stress and the operational themo-elastic stress in the AlGaN layer play a major role in determining the onset of mechanically driven device degradation. Overall, these experiments were the first to suggest that a critical level of stress may exist at which point device degradation will start to occur. The optical characterization methods developed in this study show the ability to reveal unprecedented relationships between temperature/stress and device performance/reliability. They can be used as effective tools for facilitating improvement of the reliability of future AlGaN/GaN HEMTs.